Power system for downhole toolstring

ABSTRACT

A downhole power system is provided that includes an energy storage adapted to operate at high temperatures, and a modular signal interface device that serves to control the energy storage component as well as offer a means of data logging at high temperatures. The controller is fabricated from pre-assembled components that may be selected for various combinations to provide desired functionality. The energy storage may include at least one ultracapacitor.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims the benefit of U.S. Provisional PatentApplication No. 61/896,009, filed Oct. 25, 2014; the present applicationis also a continuation in part of International Patent Application No.PCT/US2014/029992 filed Mar. 15, 2014, which in turn claims priority toU.S. patent application Ser. No. 13/843,746 filed Mar. 15, 2013, and toU.S. Provisional Patent Application No. 61/888,133 filed Oct. 8, 2013.The entire contents of each of the foregoing references is incorporatedherein by reference.

BACKGROUND OF THE INVENTION

Systems and methods directed to providing power to instruments in adownhole environment are generally described.

As people and companies continue to search for and extract oil, thequest for hydrocarbons has grown increasingly complex. For example, itis well known that the “easy oil” is generally gone, and exploration nowrequires searching to greater depths than ever before by drilling awellbore deep into the Earth. While drilling of the wellbore permitsindividuals and companies to evaluate sub-surface materials and toextract desired hydrocarbons, many problems are encountered in theseharsh environments, where downhole temperatures may range up to or inexcess of 300 degrees Celsius.

As well drilling and logging plunges ever deeper into the Earth's crust,the exposure of downhole tooling to high temperature environmentscontinues to increase. Moreover, present day instrumentation isgenerally not built to operate in such an environment, and will failwell before reaching ambient temperatures within this range. Thiscomplication has given rise to all sorts of complex instrumentation.Consistent with other segments of technology, increasing complexity ofinstrumentation presents users with increasing power demands.

In particular, elevated temperatures often present technical limitationswhere conventional systems fail. For example, conventional power systemscomprising electronics and energy storage will fail at temperaturesfound in downhole environments either due to degradation or destructionof the conventional energy storage or of the conventional electronics.Moreover, improved instrumentation systems often demand greatercapabilities of power systems.

As such, there is a growing need for power systems comprising an energystorage device for downhole operations in high temperature environmentsup to about 200 degrees Celsius, or higher. Preferably, the energystorage device would provide users with power where conventional devicesfail to provide useful power.

SUMMARY OF THE INVENTION

Accordingly, various embodiments relate to a downhole power supplysystem that includes an energy storage and, in certain embodiments, amodular signal interface device. The modular signal interface device maybe used, for example, to control the energy storage component. Incertain embodiments, the modular signal interface device can log data.The energy storage and/or the modular signal interface device may beconfigured, in some embodiments, to operate at high temperatures. Thecontroller may be fabricated from pre-assembled components that may beselected for various combinations to provide desired functionality. Theenergy storage may include at least one ultracapacitor.

In one aspect, the invention provides a system comprising an MSID, and ahousing structure configured to accommodate the MSID for placement intoa toolstring.

In another aspect, the invention provides a system comprising an MSID,and a housing structure configured to accommodate the MSID for mountingon or in the collar.

In another aspect, the invention provides a power system, the systemcomprising an MSID of the present invention; a high temperaturerechargeable energy storage device; and a housing structure in which theMSID and high temperature rechargeable energy storage device are bothdisposed for placement into a toolstring.

In another aspect, the invention provides a data system, the systemcomprising a controller adapted to receive power from a power source andconfigured for data logging; and one or more sensor circuits configuredto receive data; and wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In another aspect, the invention provides a data system, the systemcomprising a controller adapted to receive power from a power source andconfigured for drilling optimization; and one or more sensor circuitsconfigured to receive drilling data in real-time, suitable formodification of drilling dynamics; and wherein the system is adapted foroperation in a temperature range of between about seventy five degreesCelsius to about two hundred and ten degrees Celsius.

In another aspect, the invention provides a data system, the systemcomprising a controller adapted to receive power from a power source andconfigured to determine torque on bit (TOB); and one or more sensorcircuits configured to receive data; and wherein the system is adaptedfor operation in a temperature range of between about seventy fivedegrees Celsius to about two hundred and ten degrees Celsius.

In another aspect, the invention provides a data system, the systemcomprising a controller adapted to receive power from a power source andconfigured to determine weight on bit (WOB); and one or more sensorcircuits configured to receive data; and wherein the system is adaptedfor operation in a temperature range of between about seventy fivedegrees Celsius to about two hundred and ten degrees Celsius.

In another aspect, the invention provides a data system, the systemcomprising a controller adapted to receive power from a power source andconfigured to determine temperature by way of a temperature sensor(e.g., a resistance temperature detector (RTD) which indicates atemperature by way of changing resistance); one or more sensor circuitsconfigured to receive data; and wherein the system is adapted foroperation in a temperature range of between about seventy five degreesCelsius to about two hundred and ten degrees Celsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured to control the input power from the power source and outputHTRES voltage; wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured for reducing battery consumption by greater than 30%; whereinthe system is adapted for operation in a temperature range of betweenabout seventy five degrees Celsius to about two hundred and ten degreesCelsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured for increasing battery run time by greater than 50%; whereinthe system is adapted for operation in a temperature range of betweenabout seventy five degrees Celsius to about two hundred and ten degreesCelsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured for increasing the operating efficiency to greater than 90%;wherein the system is adapted for operation in a temperature range ofbetween about seventy five degrees Celsius to about two hundred and tendegrees Celsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured to draw a constant current from the battery and constantoutput voltage across the battery discharge; wherein the system isadapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius.

In another aspect, the invention provides a power system adapted forbuffering the power from a power source to a load comprising: a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured to control the input current from the power source and outputHTRES voltage; wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In another aspect, the invention provides a method of improving theefficiency of drilling dynamics comprising using any data systemdescribed herein.

In another aspect, the invention provides a method for fabricating apower system of the present invention comprising: selecting a hightemperature rechargeable energy storage (HTRES); and a controller forcontrolling at least one of charging and discharging of the energystorage, the controller comprising at least one modular circuitconfigured to control the buffering of power from a power source to aload; and incorporating the HTRES and controller into a housing, suchthat a power system described herein.

In another aspect, the invention provides a method for buffering thepower from a power source to a load comprising electrically coupling apower source to any power system of claims described herein, andelectrically coupling said power system to a load, such that the poweris buffered from the power source to the load.

In another aspect, the invention provides a method for fabricating adata system of the present invention comprising: selecting a controlleradapted to receive power from a power source and configured for datalogging, one or more sensor circuits configured to receive (e.g., andinterpret) data; and wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius; and incorporating controller andsaid sensor circuits into a housing, such that a data system of claimsdescribed herein.

In another aspect, the invention provides a method for data loggingcomprising electrically coupling a power source to any data systemdescribed herein, such that data logging is enabled.

Other advantages and novel features will become apparent from thefollowing detailed description of various non-limiting embodiments whenconsidered in conjunction with the accompanying figures. In cases wherethe present specification and a document incorporated by referenceinclude conflicting and/or inconsistent disclosure, the presentspecification shall control.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter which is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The foregoing and other features and advantages ofthe invention are apparent from the following detailed description takenin conjunction with the accompanying drawings. The accompanying figuresare schematic and are not intended to be drawn to scale. In the figures,each identical or nearly identical component illustrated is typicallyrepresented by a single numeral. For purposes of clarity, not everycomponent is labeled in every figure, nor is every component of eachembodiment shown where illustration is not necessary to allow those ofordinary skill in the art to understand the invention. In the figures:

FIG. 1 illustrates an exemplary embodiment of a drill string thatincludes a logging instrument;

FIG. 2 illustrates an exemplary embodiment for well logging with aninstrument deployed by a wireline;

FIG. 3 illustrates aspects of an exemplary ultracapacitor;

FIG. 4 depicts embodiments of primary structures for cations that may beincluded in an exemplary ultracapacitor;

FIG. 5 depicts an embodiment of a housing for an exemplaryultracapacitor;

FIG. 6 illustrates an embodiment of a storage cell for an exemplarycapacitor;

FIG. 7 depicts a barrier disposed on an interior portion of an exemplarybody of a housing;

FIGS. 8A and 8B, collectively referred to herein as FIG. 8, depictaspects of an exemplary cap for a housing;

FIG. 9 depicts an exemplary assembly of the ultracapacitor according tocertain of the teachings herein;

FIGS. 10A and 10B, collectively referred to herein as FIG. 10, depictsthe modular housing system, e.g., the 3 component housing in bothassembled (FIG. 10A) and disconnected (FIG. 10B) views;

FIG. 11 depicts a barrier disposed about a storage cell as a wrapper,according to certain embodiments;

FIGS. 12A, 12B and 12C, collectively referred to herein as FIG. 12,depict exemplary embodiments of a cap that include multi-layeredmaterials;

FIG. 13 is a cross-sectional view, according to some embodiments, of anelectrode assembly that includes a glass-to-metal seal;

FIG. 14 is a cross-sectional view of the exemplary electrode assembly ofFIG. 13 installed in the exemplary cap of FIG. 12B;

FIG. 15 depicts an exemplary arrangement of an energy storage cell inprocess of assembly;

FIGS. 16A, 16B and 16C, collectively referred to herein as FIG. 16,depict certain embodiments of an assembled energy storage cell;

FIG. 17 depicts use of polymeric insulation over an exemplary electrodeassembly;

FIGS. 18A, 18B and 18C, collectively referred to herein as FIG. 18,depict aspects of an exemplary template for another embodiment of thecap for the energy storage;

FIG. 19 is a perspective view of an electrode assembly, according tocertain embodiments, that includes hemispherically shaped material;

FIG. 20 is a perspective view of an exemplary cap including theelectrode assembly of FIG. 19 installed in the template of FIG. 18C;

FIG. 21 is a cross-sectional view of the cap of FIG. 20;

FIG. 22 is a transparent isometric view of an exemplary energy storagecell disposed in a cylindrical housing;

FIG. 23 is an isometric view of an embodiment of an exemplary energystorage cell prior to being rolled into a rolled storage cell;

FIG. 24 is a side view of a storage cell, showing the various layers ofone embodiment;

FIG. 25 is an isometric view of a rolled storage cell, according to someembodiments, which includes a reference mark for placing a plurality ofleads;

FIG. 26 is an isometric view of the exemplary storage cell of FIG. 25with reference marks prior to being rolled;

FIG. 27 depicts an exemplary rolled up storage cell with the pluralityof leads included;

FIG. 28 depicts, according to certain embodiments, a Z-fold impartedinto aligned leads (i.e., a terminal) coupled to a storage cell;

FIG. 29 depicts an exemplary ultracapacitor string, as described herein,highlighting certain components of assembly;

FIG. 30 depicts an exemplary ultracapacitor string in a 3 strand packassembly of ultracapacitors;

FIG. 31A depicts a cell assembly without excess internal space;

FIG. 31B depicts a cell assembly with excess internal space;

FIG. 32 depicts modular board stackers as bus connectors, comprisingheaders and receptacles;

FIG. 33 depicts aspects of an ultracapacitor management system;

FIG. 34 depicts an exemplary embodiment of a system disclosed herein;

FIG. 35 depicts a flow diagram relating to communication protocols;

FIG. 36 depicts a circuit model of a motor;

FIG. 37 depicts a flow diagram relating to motor control;

FIGS. 38A and 38B, collectively referred to herein as FIG. 38, depictconfigurations of accelerometers; and

FIG. 39 depicts a downhole system with a cut away from the housingshowing the internal components.

FIGS. 40A and 40B, collectively referred to herein as FIG. 40, depictexemplary current and voltage data illustrating the MSID-based devices,system, and methods disclosed herein.

FIGS. 41A and 41B are schematic of a tool string and associated downholepower supply system. FIG. 41A does not induce an energy storage device(ESD). FIG. 41B includes an ESD.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are various configurations of a downhole system thatincludes an energy storage and, in certain embodiments, a modular signalinterface device. The modular signal interface device may be used, forexample, to control the energy storage component. In certainembodiments, the modular signal interface device can log data. Theenergy storage and/or the modular signal interface device may beconfigured, in some embodiments, to operate at high temperatures. Thesystems, some of which may be power systems, provide users with greatercapabilities than previously achieved downhole. Such systems, whileshown specifically for use in downhole environments, may be used for anyapplication where similar environments exist, such as enginecompartments of planes, cars, etc, or energy production plants/turbines.However, in order to provide context for the downhole power systems andmethods for use, some background information and definitions areprovided.

The systems disclosed herein may be used in various non-limitingapplications as outlined below:

1) During Drilling Operations

a) While Drilling

i) MWD

ii) LWD

b) Wireline Logging

i) Electric Line

ii) Memory Logging

2) During Completion Operations

a) Wireline Logging

i) Electric Line

ii) Memory Logging

3) During Production Operations

a) Permanent Logging

b) Wireline Logging

i) Electric Line

ii) Memory Logging

Refer now to FIG. 1 where aspects of an apparatus for drilling awellbore 101 (also referred to as a “borehole”) are shown. As a matterof convention, a depth of the wellbore 101 is described along a Z-axis,while a cross-section is provided on a plane described by an X-axis anda Y-axis.

In this example, the wellbore 101 is drilled into the Earth 102 using adrill string 111 driven by a drilling rig (not shown) which, among otherthings, provides rotational energy and downward force. The wellbore 101generally traverses sub-surface materials, which may include variousformations 103 (shown as formations 103A, 103B, 103C). One skilled inthe art will recognize that the various geologic features as may beencountered in a subsurface environment may be referred to as“formations,” and that the array of materials down the borehole (i.e.,downhole) may be referred to as “sub-surface materials.” That is, theformations 103 are formed of sub-surface materials. Accordingly, as usedherein, it should be considered that while the term “formation”generally refers to geologic formations, and “sub-surface material,”includes any materials, and may include materials such as solids,fluids, gases, liquids, and the like.

In this example, the drill string 111 includes lengths of drill pipe 112which drive a drill bit 114. The drill bit 114 also provides a flow of adrilling fluid 104, such as drilling mud. The drilling fluid 104 isoften pumped to the drill bit 114 through the drill pipe 112, where thefluid exits into the wellbore 101. This results in an upward flow, F, ofdrilling fluid 104 within the wellbore 101. The upward flow, F,generally cools the drill string 111 and components thereof, carriesaway cuttings from the drill bit 114 and prevents blowout of pressurizedhydrocarbons 105.

The drilling fluid 104 (also referred to as “drilling mud”) generallyincludes a mixture of liquids such as water, drilling fluid, mud, oil,gases, and formation fluids as may be indigenous to the surroundings.Although drilling fluid 104 may be introduced for drilling operations,use or the presence of the drilling fluid 104 is neither required fornor necessarily excluded from well logging operations. Generally, alayer of materials will exist between an outer surface of the drillstring 111 and a wall of the wellbore 101. This layer is referred to asa “standoff layer,” and includes a thickness, referred to as “standoff,S.”

The drill string 111 generally includes equipment for performing“measuring while drilling” (MWD), also referred to as “logging whiledrilling” (LWD). Performing MWD or LWD generally calls for operation ofa logging instrument 100 that in incorporated into the drill string 111and designed for operation while drilling. Generally, the logginginstrument 100 for performing MWD is coupled to an electronics packagewhich is also on board the drill string 111, and therefore referred toas “downhole electronics 113.” Generally, the downhole electronics 113provides for at least one of operational control and data analysis.Often, the logging instrument 100 and the downhole electronics 113 arecoupled to topside equipment 107. The topside equipment 107 may beincluded to further control operations, provide greater analysiscapabilities, and/or log data, and the like. A communications channel(not shown) may provide for communications to the topside equipment 107,and may operate via pulsed mud, wired pipe, and/or any othertechnologies as are known in the art.

Generally, data from the MWD apparatus provide users with enhancedcapabilities. For example, data made available from MWD evolutions maybe useful as inputs to geosteering (i.e., steering the drill string 111during the drilling process) and the like.

Referring now to FIG. 2, an exemplary logging instrument 100 forwireline logging of the wellbore 101 is shown. As a matter ofconvention, a depth of the wellbore 101 is described along a Z-axis,while a cross-section is provided on a plane described by an X-axis anda Y-axis. Prior to well logging with the logging instrument 100, thewellbore 101 is drilled into the Earth 102 using a drilling apparatus,such as the one shown in FIG. 1.

In some embodiments, the wellbore 101 has been filled, at least to someextent, with drilling fluid 104. The drilling fluid 104 (also referredto as “drilling mud”) generally includes a mixture of liquids such aswater, drilling fluid, mud, oil, gases, and formation fluids as may beindigenous to the surroundings. Although drilling fluid 104 may beintroduced for drilling operations, use or the presence of the drillingfluid 104 is neither required for nor necessarily excluded from loggingoperations during wireline logging. Generally, a layer of materials willexist between an outer surface of the logging instrument 100 and a wallof the wellbore 101. This layer is referred to as a “standoff layer,”and includes a thickness, referred to as “standoff, S.”

Generally, the logging instrument 100 is lowered into the wellbore 101using a wireline 108 deployed by a derrick 106 or similar equipment.Generally, the wireline 108 includes suspension apparatus, such as aload bearing cable, as well as other apparatus. The other apparatus mayinclude a power supply, a communications link (such as wired or optical)and other such equipment. Generally, the wireline 108 is conveyed from aservice truck 109 or other similar apparatus (such as a service station,a base station, etc,). Often, the wireline 108 is coupled to topsideequipment 107. The topside equipment 107 may provide power to thelogging instrument 100, as well as provide computing and processingcapabilities for at least one of control of operations and analysis ofdata.

Generally, the logging instrument 100 includes a power supply 115. Thepower supply 115 may provide power to downhole electronics 113 (i.e.,power consuming devices) as appropriate. Generally, the downholeelectronics 113 provide measurements and/or perform sampling and/or anyother sequences desired to locate, ascertain and qualify a presence ofhydrocarbons 105.

The present invention, including the modular signal interface devices,and related power systems and uses thereof will be described withreference to the following definitions that, for convenience, are setforth below. Unless otherwise specified, the below terms used herein aredefined as follows:

DEFINITIONS

When introducing elements of the present invention or the embodiment(s)thereof, the articles “a,” “an,” and “the” are intended to mean thatthere are one or more of the elements. Similarly, the adjective“another,” when used to introduce an element, is intended to mean one ormore elements. The terms “including,” “has” and “having” are intended tobe inclusive such that there may be additional elements other than thelisted elements.

The language “and/or” is used herein as a convention to describe either“and” or “or” as separate embodiments. For example, in a listing of A,B, and/or C, it is intended to mean both A, B, and C; as well as A, B,or C, wherein each of A, B, or C is considered a separate embodiment,wherein the collection of each in a list is merely a convenience. Asused herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e. “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.” “Consisting essentially of,” when used in the claims,shall have its ordinary meaning as used in the field of patent law.

The terms “alkenyl” and “alkynyl” are recognized in the art and refer tounsaturated aliphatic groups analogous in length and possiblesubstitution to the alkyls described below, but that contain at leastone double or triple bond respectively.

The term “alkyl” is recognized in the art and may include saturatedaliphatic groups, including straight-chain alkyl groups, branched-chainalkyl groups, cycloalkyl (alicyclic) groups, alkyl substitutedcycloalkyl groups, and cycloalkyl substituted alkyl groups. In certainembodiments, a straight chain or branched chain alkyl has about 20 orfewer carbon atoms in its backbone (e.g., C₁-C₂₀ for straight chain,C₁-C₂₀ for branched chain). Likewise, cycloalkyls have from about 3 toabout 10 carbon atoms in their ring structure, and alternatively about5, 6 or 7 carbons in the ring structure. Examples of alkyl groupsinclude, but are not limited to, methyl, ethyl, propyl, butyl, pentyl,hexyl, ethyl hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl andthe like.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from any one or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

The expression “back EMF” is art recognized and describes the inducedvoltage that varies with the speed and position of the rotor.

The term “buffer” as used herein, when used in the context of a systemas described herein, e.g. a power system as described herein, generallyrelates to a decoupling of an aspect (e.g., at least one aspect) of afirst input or output of said system from one aspect of second input oroutput of said system. Exemplary aspects include voltage, current,power, frequency, phase, and the like. The terms buffering, buffer,power buffer, source buffer and the like as used herein generally relateto the concept of the buffer as defined above.

As used herein, the term “cell” refers to an ultracapacitor cell.

As used herein, the terms “clad,” “cladding” and the like refer to thebonding together of dissimilar metals. Cladding is often achieved byextruding two metals through a die as well as pressing or rolling sheetstogether under high pressure. Other processes, such as laser cladding,may be used. A result is a sheet of material composed of multiplelayers, where the multiple layers of material are bonded together suchthat the material may be worked with as a single sheet (e.g., formed asa single sheet of homogeneous material would be formed).

As a matter of convention, it may be considered that a “contaminant” maybe defined as any unwanted material that may negatively affectperformance of the ultracapacitor 10 if introduced. Also note, thatgenerally herein, contaminants may be assessed as a concentration, suchas in parts-per-million (ppm). The concentration may be taken as byweight, volume, sample weight, or in any other manner as determinedappropriate.

As used herein, use of the term “control” with reference to the powersupply generally relates to governing performance of the power supply.However, in some embodiments, “control” may be construed to providemonitoring of performance of the power supply. The monitoring may beuseful, for example, for otherwise controlling aspects of use of thepower supply (e.g., withdrawing the power supply when a state-of-chargeindicates useful charge has been expended). Accordingly, the terms“control,” “controlling” and the like should be construed broadly and ina manner that would cover such additional interpretations as may beintended or otherwise indicated.

The term “cyano” is given its ordinary meaning in the art and refers tothe group, CN. The term “sulfate” is given its ordinary meaning in theart and refers to the group, SO₂. The term “sulfonate” is given itsordinary meaning in the art and refers to the group, SO₃X, where X maybe an electron pair, hydrogen, alkyl or cycloalkyl. The term “carbonyl”is recognized in the art and refers to the group, C═O.

The language “downhole conditions” or “downhole environments” may beused interchangeably herein to describe the general conditionsexperienced for equipment subjected to environments comprising hightemperatures, e.g., greater than 75 degrees Celsius, e.g., greater than100 degrees Celsius, e.g., greater than 125 degrees Celsius, e.g.,greater than 150 degrees Celsius, e.g., greater than 175 degreesCelsius, e.g., greater than 200 degrees Celsius, and/or shock andvibrations greater than 5 G, e.g. greater than 10 G, e.g. greater than20 G, e.g. greater than 50 G, e.g. greater than 100 G.

“Energy density” is one half times the square of a peak device voltagetimes a device capacitance divided by a mass or volume of said device.

As discussed herein, “hermetic” refers to a seal whose quality (i.e.,leak rate) is defined in units of “atm-cc/second,” which means one cubiccentimeter of gas (e.g., He) per second at ambient atmospheric pressureand temperature. This is equivalent to an expression in units of“standard He-cc/sec.” Further, it is recognized that 1 atm-cc/sec isequal to 1.01325 mbar-liter/sec.

The terms “heteroalkenyl” and “heteroalkynyl” are recognized in the artand refer to alkenyl and alkynyl alkyl groups as described herein inwhich one or more atoms is a heteroatom (e.g., oxygen, nitrogen, sulfur,and the like).

The term “heteroalkyl” is recognized in the art and refers to alkylgroups as described herein in which one or more atoms is a heteroatom(e.g., oxygen, nitrogen, sulfur, and the like). For example, alkoxygroup (e.g., —OR) is a heteroalkyl group.

The term “heuristics” is art-recognized, and generally describesexperience-based techniques for problem solving.

As a matter of convention, the terms “internal resistance” and“effective series resistance” and “ESR”, terms that are known in the artto indicate a resistive aspect of a device, are used interchangeablyherein.

As a matter of convention, the term “leakage current” generally refersto current drawn by the capacitor which is measured after a given periodof time. This measurement is performed when the capacitor terminals areheld at a substantially fixed potential difference (terminal voltage).When assessing leakage current, a typical period of time is seventy two(72) hours, although different periods may be used. It is noted thatleakage current for prior art capacitors generally increases withincreasing volume and surface area of the energy storage media and theattendant increase in the inner surface area of the housing. In general,an increasing leakage current is considered to be indicative ofprogressively increasing reaction rates within the ultracapacitor 10.Performance requirements for leakage current are generally defined bythe environmental conditions prevalent in a particular application. Forexample, with regard to an ultracapacitor 10 having a volume of 20 mL, apractical limit on leakage current may fall below 200 mA.

A “lifetime” for the capacitor is also generally defined by a particularapplication and is typically indicated by a certain percentage increasein leakage current or degradation of another parameter such ascapacitance or internal resistance (as appropriate or determinative forthe given application). For instance, in one embodiment, the lifetime ofa capacitor in an automotive application may be defined as the time atwhich the leakage current increases to 200% of its initial (beginning oflife or “BOL”) value. In another example, the lifetime of a capacitor inan oil and gas application may be defined as the time at which any ofthe following occurs: the capacitance falls to 50% of its BOL value, theinternal resistance increases to 200% of its BOL value, the leakageincreases to 200% of its BOL value. As a matter of convention, the terms“durability” and “reliability” of a device when used herein generallyrelate to a lifetime of said device as defined above.

The term “modular bus” is used herein as a convention to describe theprotocol of board topology and pin assignment on each circuit boardwhich supports the flow of power and that affords it the capability tocommunicate to the other circuits and/or external hardware through thealigned stackers connecting the boards.

An “operating temperature range” of a device generally relates to arange of temperatures within which certain levels of performance aremaintained and is generally determined for a given application. Forinstance, in one embodiment, the operating temperature range for an oiland gas application may be defined as the temperature range in which theresistance of a device is less than about 1,000% of the resistance ofsaid device at 30 degrees Celsius, and the capacitance is more thanabout 10% of the capacitance at 30 degrees Celsius.

In some instances, an operating temperature range specification providesfor a lower bound of useful temperatures whereas a lifetimespecification provides for an upper bound of useful temperatures.

The terms “optimization” and “optimize” are used herein to describe theprocess of moving a system or performance towards an improved system orperformance as compared to a system or performance without the object ormethod that is being recited as causing the optimization. For clarity,it is not intended herein to suggest that by using these terms, that themost optimum value must be achieved; as such it should be understoodthat the an optimized range is on a spectrum of improvement.

“Peak power density” is one fourth times the square of a peak devicevoltage divided by an effective series resistance of said device dividedby a mass or volume of said device.

The term “signal,” as used herein, describes the transference of energyor data over time. Moreover, unless specified otherwise, the term signalwill mean either energy transference over time, or data transferenceover time.

The term “subsurface” as used herein, refers to an environment below thesurface of the earth or an environment having similar characteristics.

The term “system” or “systems” are used herein to include power systems,data logging systems, or a combination thereof.

The term “ultracapacitor” as used herein, describes an energy storagedevice exploiting art-recognized eletrolytic double layer capacitancemechanisms.

As referred to herein, a “volumetric leakage current” of theultracapacitor 10 generally refers to leakage current divided by avolume of the ultracapacitor 10, and may be expressed, for example inunits of mA/cc. Similarly, a “volumetric capacitance” of theultracapacitor 10 generally refers to capacitance of the ultracapacitor10 divided by the volume of the ultracapacitor 10, and may be expressed,for example in units of F/cc. Additionally, “volumetric ESR” of theultracapacitor 10 generally refers to ESR of the ultracapacitor 10multiplied by the volume of the ultracapacitor 10, and may be expressed,for example in units of Ohms·cc.

As a matter of convention, it should be considered that the term “may”as used herein is to be construed as optional; “includes” is to beconstrued as not excluding other options (i.e., steps, materials,components, compositions, etc,); “should” does not imply a requirement,rather merely an occasional or situational preference. Other similarterminology is likewise used in a generally conventional manner.

As discussed herein, terms such as “adapting,” “configuring,”“constructing” and the like may be considered to involve application ofany of the techniques disclosed herein, as well as other analogoustechniques (as may be presently known or later devised) to provide anintended result.

Applications of the Present Invention

One skilled in the art will recognize that the systems of the presentinvention may be used in conjunction with technologies andinstrumentation in support of resistivity, nuclear including pulsedneutron and gamma measuring as well as others, magnetic resonanceimaging, acoustic, and/or seismic measurements, formation samplingtools, various sampling protocols, communications, data processing andstorage, geo-steering, rotary steerable tools, accelerometers,magnetometers, sensors, transducers, digital and/or analog devices(including those listed below) and the like and a myriad of othersystems having requirements for power use downhole. A great complimentof components may also be powered by the power systems of the presentinvention. Non-limiting examples include accelerometers, magnetometers,sensors, transducers, digital and/or analog devices (including thoselisted below) and the like. Other examples include rotary steerabletools. Other examples include telemetry components or systems such asmud-pulse telemetry systems. Non-limiting examples of mud pulsetelemetry systems include rotary mud pulsers, solenoid driven mudpulsers, and motor driven mud pulsers. Other non-limiting examples oftelemetry systems include EM telemetry systems, wired telemetry systems,fiber optic telemetry systems and the like.

The power source may include a variety of energy inputs. The energyinputs may be generally divided into three categories. The categoriesinclude batteries, remote systems, and generators.

In some embodiments, the power source includes a primary battery.Exemplary batteries include those that are adapted for operation in aharsh environment. Specific examples include various chemical batteries,including those with lithium. More specific examples includelithium-thionyl-chloride (Li—SOCl₂) and batteries based on similartechnologies and/or chemistries. However, it is recognized that some ofthese technologies may not be capable of achieving the desiredtemperature ratings, and that some of these technologies may onlysupport the energy storage on a short term basis (i.e., the energystorage may include, for example, elements that are not rechargeable, orthat have a shortened life when compared with other elements). Otherexemplary batteries that may be included includelithium-bromine-chloride, as well as lithium-sulfuryl-chloride and fusedsalt.

The power source may include at least one connection to a remote powersupply. That is, energy may be supplied via an external source, such asvia wireline. Given that external energy sources are not constrained bythe downhole environment, the primary concern for receiving energyincludes methods and apparatus for communicating the energy downhole.Exemplary techniques for communicating energy to the systems of thepresent invention include wired casing, wired pipe, coiled tubing andother techniques as may be known in the art.

The power source may include at least one generator. Various types ofenergy generation devices may be used alone or in combination with eachother, Exemplary types of energy generators include, without limitation,rotary generators, electromagnetic displacement generators,magnetostritive displacement generators, piezoelectric displacementgenerators, thermoelectric generators, thermophotovoltaic generators,and may include connections to remote generators, such as a wirelineconnection to a generator or power supply that is maintained topside.Other types of generators include inertial energy generators, linearinertial energy generators, rotary inertial energy generators, orvibration energy generators.

As mentioned above, other types of generators include, withoutlimitation, rotary generators, electromagnetic displacement generators,magnetostrictive displacement generators, piezoelectric displacementgenerators, thermoelectric generators, thermophotovoltaic generators,and may include connections to remote generators, such as a wirelineconnection to a generator or power supply that is maintained topside,and a radioisotope power generator.

Rotary types of generators may include, for example, generators thatrely on fluid (liquid or gas or a mixture) induced rotation, asingle-stage design, a multi-stage and may be redundant.

Electromagnetic displacement types of generation may rely upon, forexample, drill string vibration (wanted or unwanted), acousticvibration, seismic vibration, flow-induced vibration (such as from mud,gas, oil, water, etc.) and may include generation that is reliant uponreciprocating motion.

Magnetostrictive types of generation are reliant on magnetostriction,which is a property of ferromagnetic materials that causes them tochange their shape or dimensions during the process of magnetization.Magnetostrictive materials can convert magnetic energy into kineticenergy, or the reverse, and are used to build actuators and sensors. Aswith electromagnetic displacement types of generation, magnetostrictivetypes of generation may rely upon, for example, drill string vibration(wanted or unwanted), acoustic vibration, seismic vibration,flow-induced vibration (such as from mud, gas, oil, water, etc.) and mayinclude generation that is reliant upon reciprocating motion, as well asother techniques that generate or result in a form of kinetic ormagnetic energy.

Piezoelectric types of generation are reliant on materials that exhibitpiezoelectric properties. Piezoelectricity is the charge thataccumulates in certain solid materials (notably crystals, certainceramics, and the like) in response to applied mechanical stress.Piezoelectric types of generation may rely upon, for example, drillstring vibration (wanted or unwanted), acoustic vibration, seismicvibration, flow-induced vibration (such as from mud, gas, oil, water,etc.) and may include generation that is reliant upon reciprocatingmotion, as well as other techniques that generate or result in a form ofmechanical stress.

The piezoelectric effect can be utilized to convert mechanical energyinto electrical energy. For example, a piezoelectric element may beconstructed in the form of a cantilevered beam, whereby movement of theend of the beam bends the beam under vibration. The piezoelectricelement may also be constructed as a platter, whereby vibration causesdistortion in the center of the platter. In each configuration, varyingmass loads may be used to enhance the effect of the mechanicalvibration. For instance, a mass may be placed on the end of thecantilevered beam to increase the level of deflection incurred on thebeam caused by mechanical vibration of the system.

In some embodiments, a piezoelectric electric generator includes one tomany piezoelectric elements, each element provided to convert mechanicalenergy into electrical current. The piezoelectric electric generator mayalso include one to many conducting elements to transfer the electricalcurrent to energy conversion or storage electronics. Each piezoelectricgenerator may be configured in plurality to enhance energy generationcapabilities. The piezoelectric generators may be placed in suitabledirections to capture various modes of mechanical vibration. Forinstance, in order to capture three dimensions of lateral vibration, thepiezoelectric generators may be placed orthogonal to each other suchthat each dimension of vibration is captured by at least one set ofpiezoelectric generators.

Generally, piezoelectric generators are useful for generating up to awatt of electric power. However, multiple generators may be used inparallel to generate additional power. In one embodiment, a single massmay be configured to deform multiple piezoelectric elements at a giventime.

Like the electromagnetic generators, piezoelectric generators operatewith a given natural frequency. The most power is generated when themechanical vibration occurs at the natural frequency of thepiezoelectric generator. In order to maximize the amount of generatedpower, the natural frequency of the piezoelectric generator may betuned, as previously discussed, by including varying load elements tothe conducting material. In another embodiment, there may be multiplepiezoelectric generators tuned to different fixed frequencies to capturea range of vibration frequencies. Dampening in the form of a materialattached to the piezoelectric element or a fluid surrounding thepiezoelectric element may be used to broaden the effective capturespectrum of the piezoelectric generator while decreasing the resonantresponse.

In one embodiment where the mechanical energy source is in the form offluid flow, a rotation based piezoelectric generator may be used. Forexample, one to many piezoelectric elements may be deformed due to therotation of a structure. In one embodiment, one to many piezoelectricbeams may be bent by orthogonal pins attached to a rotating wheel. Asthe wheel rotates around its axis, the pins contact the piezoelectricelements and cause deformation of the elements as the wheel rotates. Inanother embodiment, piezoelectric elements are placed parallel to andadjacent to a rotating body of varying radii. As the rotating bodyrotates, the piezoelectric elements are compressed to varying degreesdepending on the radius at the contact point between the rotating bodyand the piezoelectric element. In this embodiment, there may bepiezoelectric elements also placed on the rotating body to produceadditional electrical energy.

Thermoelectric types of generation are reliant on materials that exhibitthermoelectric properties. Thermoelectric generators generally convertheat flow (temperature differences) directly into electrical energy,using a phenomenon called the “Seebeck effect” (or “thermoelectriceffect”). Exemplary thermoelectric generators may rely on bimetallicjunctions (a combination of materials) or make use of particularthermoelectric materials. One example of a thermoelectric material isbismuth telluride (Bi₂Te₃), a semiconductor with p-n junctions that canhave thicknesses in the millimeter range. Generally, thermoelectricgenerators are solid state devices and have no moving parts.

Thermoelectric generators may be provided to take advantage of varioustemperature gradients. For example, a temperature differential insideand outside of pipe, a temperature differential inside and outside ofcasing, a temperature differential along drill string, a temperaturedifferential arising from power dissipation within tool (from electricaland/or mechanical energy), and may take advantage of induced temperaturedifferentials.

Thermophotovoltaic generators provide for energy conversion of heatdifferentials to electricity via photons. In a simple form, thethermophotovoltaic system includes a thermal emitter and a photovoltaicdiode cell. While the temperature of the thermal emitter varies betweensystems, in principle, a thermophotovoltaic device can extract energyfrom any emitter with temperature elevated above that of thephotovoltaic device (thus forming an optical heat engine). The emittermay be a piece of solid material or a specially engineered structure.Thermal emission is the spontaneous emission of photons due to thermalmotion of charges in the material. In the downhole environment, ambienttemperatures cause radiation mostly at near infrared and infraredfrequencies. The photovoltaic diodes can absorb some of these radiatedphotons and convert them into electrons.

Other forms of power generation may be used. For example, radioisotopepower generation may be incorporated into the power supply, whichconverts ions into a current.

A variety of techniques may be employed for incorporating the foregoingtypes of power generators into the drill string. For example,piezoelectric elements may be included into a design in order to supplyintermittent or continuous power to electronics. The down-holeenvironment offers numerous opportunities for piezoelectric powergeneration due to the abundance of vibration, either wanted or unwanted,through acoustic, mechanical, or seismic sources.

There are three primary modes of vibration in a down-hole drill string;drill collar whirl, bit bounce, and collar stick-slip. Each of thesemodes is capable of coupling into each other, causing lateral,torsional, and axial vibrations.

In a down-hole instrument, there are numerous locations that offer apotential for energy harvesting. The instrument may be composed ofseparate sections that are directly connected through rigid supports,left connected through a flexible connection, or left unconnected bymaterial other than piezoelectric elements. A flexible connection may becomprised of a flexible membrane or pivoting rigid structure.

To capture energy from torsional vibration, piezoelectric material canbe placed vertically along the length of the instrument. Torsionalstresses between sections of the instrument may cause the piezoelectricelement to deform. A conducting material can be placed along thepiezoelectric element to carry generated current to energy storage orconversion devices.

In another embodiment, piezoelectric material can be utilized togenerate energy from axial vibration. For instance, piezoelectricelement can be placed between two or more compartments that areotherwise left unconnected or connected flexible connection. Each end ofthe piezoelectric element may be connected to the surface of theinstrument orthogonal to the axial and tangential direction such thataxial vibration will compress or extend the piezoelectric element.

In another embodiment, piezoelectric material can be utilized togenerate energy from lateral vibration. For instance, piezoelectricelement may be placed between two or more compartments that areotherwise left unconnected or connected via a flexible connection. Theends of the piezoelectric elements may be attached to the tangentialwalls of each compartment such that relative shear movement of eachcompartment bends the connecting piezoelectric elements.

One or many of these embodiments may be included into the sameinstrument to enhance energy generation.

In short, the power supply may make use of any type of power generatorthat may be adapted for providing power in the downhole environment. Thetypes of power generation used may be selected according to the needs orpreferences of a system user, designer, manufacturer or other interestedparty. A type of power generation may be used alone or in conjunctionwith another type of power generation.

It should be noted that as in the case of the vibrational energygenerator, other forms of generators may also be controlled (i.e.,tuned) to improve efficiency according to environmental factors. In eachcase, it is considered that “tuning” of the generator is designed toaccomplish this task. In some cases, tuning is provided during assembly.In some additional embodiments, tuning is performed on a real-time, ornear real-time basis during operation of the power supply.

Embodiments of a HTRES are disclosed herein. Before turning to thedetails of the HTRES disclosed herein, additional embodiments of HTRESinclude, without limitation, chemical batteries, aluminum electrolyticcapacitors, tantalum capacitors, ceramic and metal film capacitors,hybrid capacitors magnetic energy storage, for instance, air core orhigh temperature core material inductors. Other types of that may alsobe suitable include, for instance, mechanical energy storage devices,such as fly wheels, spring systems, spring-mass systems, mass systems,thermal capacity systems (for instance those based on high thermalcapacity liquids or solids or phase change materials), hydraulic orpneumatic systems. One example is the high temperature hybrid capacitoravailable from Evans Capacitor Company Providence, R.I. USA part numberHC2D060122 DSCC10004-16 rated for 125 degrees Celsius. Another exampleis the high temperature tantalum capacitor available from EvansCapacitor Company Providence, R.I. USA part number HC2D050152HT rated to200 degrees Celsius. Yet another example is an aluminum electrolyticcapacitor available from EPCOS Munich, Germany part numberB41691A8107Q7, which is rated to 150 degrees Celsius. Yet anotherexample is the inductor available from Panasonic Tokyo, Japan partnumber ETQ-P5M470YFM rated for 150 degrees Celsius. Additionalembodiments are available from Saft, Bagnolet, France (part numberLi-ion VL 32600-125) operating up to 125 degrees Celsius with 30charge-discharge cycles, as well as a li-ion battery (experimental)operable up to about 250 degrees Celsius, and in experimental phase withSadoway, Hu, of Solid Energy in Cambridge, Mass.

Modular Signal Interface Devices (MSID) of the Present Invention

In one embodiment of the invention, downhole electronics are controlledand/or monitored by a modular signal interface device (MSID) of thepresent invention. In certain embodiments, this MSID may serve to (1)control an energy storage component of a high temperature power system,e.g., a downhole power supply system, affording benefits such asincreased battery consumption efficiency, higher power capability, powerbuffering improved reliability through voltage stability, among otherbenefits, (2) offer a means of data logging, or (3) both. This modulardevice may be fabricated from pre-assembled components, which may beattached in a modular fashion, and which may be selected from variouscombinations to provide desired functionality. Moreover, any energystorage component may include at least one high temperature rechargeableenergy storage (HTRES) described herein, wherein any HTRES may compriseat least one high temperature ultracapacitor (HTUCap) described herein.

The modular architecture of the MSID improves the ease ofmanufacturability, and as such, affords an accelerated rate ofmanufacture of the systems of the present invention, and thereforereduces cost of production. In addition, the modular architecture of theMSID improves the ease of adding functionality as well asserviceability, which serves to reduce cost of maintenance or upgradingof functionality. Modularity also serves to reduce the design and debugcycle as circuits can be rapidly connected and disconnected foranalysis. Within the framework of the modular systems described herein,new designs and functionality may quickly be added without the need forsubstantial changes in wiring, dimensioning, or circuit board layout.

The modular design comprises several aspects of modularity. A system ofthe present invention may comprise at least one, for instance, twomodules, each designed to perform a certain function or to provide acertain aspect, and the modules may comprise distinct housings, and theymay interface with each other at a connector interface. In someembodiments, said connector interface comprises a connector housing anda connector comprising one of pins or receptacles. In some embodimentsvarious modules are configured to connect with each other by way ofmating connectors. In some embodiments one module comprises an MSIDcomprising power system components and/or data system components, e.g.circuits and another module comprises an HTRES and a housing, e.g.wherein said HTRES comprises at least one ultracapacitor, e.g. anultracapacitor string.

The modular design of the MSID derives at its core the use of aparticular circuit board architecture, starting from the reduced sizedcircular circuit boards, that are electrically connected by stackersthat afford a uniformity and modularity, wherein electricalcommunication is funneled through a modular bus, which in certainembodiments is connected to a junction circuit board that may aid inrelating the MSID to external devices, the functions of each circuit maybe locally controlled by a supervisor, which can simplify the interfacebetween circuits interfacing the modular bus, and the total circuitboard combination may be contained in a tool string space efficienthousing designed to incorporate the MSID, or the MSID and any HTRES of apower system.

Circuit boards may comprise digital supervisors for simplifying orotherwise aiding the modular bus. For instance, a circuit designed for acertain function may comprise components not easily adaptable to astandard assignment of signals on pins of a modular bus or severaldifferent circuits may comprise components that are not easily adaptableto one another on a shared modular bus. A digital supervisor disposed oncircuit boards interfacing a modular bus may serve to adapt saidcomponents to the shared modular bus. Specifically, and by way ofexample, digital supervisors may be assigned a digital identificationand establish a shared communication on a modular bus. Digitalsupervisors may receive instructions from other supervisors or fromanother controller and control the function of their respective circuitsaccordingly. As another example, digital supervisors may interrogate ormeasure an aspect of their respective circuits and report thatinformation to the shared modular bus as a digital signal. Examples ofdigital supervisors include microcontrollers, for instance the 16Fseries available from Microchip Technology Inc.

The modular signal interface devices of the present invention, useful inpower systems and/or data interfaces for data logging, may be comprisedof the following components:

1. Circuit Boards

The modular design of the MSID generally incorporates circular shapedcircuit boards, which allow for an increase in (or maximization of)circuit/power and signal density compared to that for common rectangulardesigns would provide for in a cylindrical volume, i.e., the cylindricalhousing. These circuit boards are generally made of high temperaturelaminate (e.g. p95/p96 polyimide) with a high glass transitiontemperature (e.g. T_(g)=260° C.) to ensure structural integrity at theoperating temperature (125° C.-150° C.). In addition, the boards maycontain (4 or more) layers of copper to improve thermal performance.

2. Stackers

In certain embodiments, the modular architecture utilizes board stackersas bus connectors, comprising headers and receptacles, as shown in FIG.32, which provide a way of easily and conveniently electricallyconnecting and disconnecting circuit boards. The stackers aretopologically positioned in the circuit architecture to afford alignmentand repeatable positioning of the top and bottom stackers, such that allcircuits abiding by the modular architecture are mechanically compatibleand fit together. Moreover, the stackers are selected based on theirutility at temperatures greater than 75 degrees Celsius, e.g., greater125 degrees Celsius, e.g., greater than 150 degrees Celsius, and theirability to establish contact with the mating pin of the header withoutloss of structural strength, e.g., by the engagement of a spring clip ortwist pin or the like into the mating receptacle. In a particularembodiment, the stackers are metallic and configured to providestructural strength when subjected to mechanical vibration and shock inaddition to heat, as is the case in a downhole drilling. In specificembodiments, the stacker connection apparatus is miniature to matchrelatively smaller sized circuit boards.

In addition, in certain embodiments, electrical redundancy is employedto mitigate the effects of a disconnection if one were to occur. Inparticular embodiments, the power lines have multiple redundant lines inthe stackers. For instance, the capacitor string connection to theelectronics may be carried over two pins for increased reliability, andreduced line resistance resulting in less energy loss and greater peakpower.

With respect to firmware, communication is also made possible by thestacker hardware. Because of the limited amount of space there are manycommunication protocols that would be unsuitable for architecture due tothe requirement of many lines to communicate. In certain embodiments,the communication protocol that is incorporated in the MSID comprises asynchronous communication protocol that utilizes four lines that canaddress an unlimited number of peripherals: (1) Data: Binary signal; (2)Clock: Used to trigger data capture on the data line; (3) Poll: Anadditional signal to control data direction and simplify hardware; and(4) Ground: System-wide node common to all circuits.

In addition, in certain embodiments, the MSID is configured withstandoffs disposed between the circuit boards for increased structuralintegrity. Generally, the standoff supports provide a rigid supportmaintaining spacing between each circuit. Each of the standoff supportsmay be fabricated from materials as appropriate, such as metallicmaterials and/or insulative materials, such as forms of polymers.

In some embodiments, circuits of the present invention may be circular.In some embodiments, circuits of the present invention may be stackable.In some embodiments, circuits of the present invention may be stacked.In some embodiments, circuits of the present invention may be circularand stackable and/or stacked.

3. Junction Circuit Board

Furthermore, in certain embodiments, the MSID comprises a junctioncircuit board, which eases manufacturability and serviceability and mayprovide electrical protection. The junction circuit board can providefor electrically connecting circuit boards to end connectors of thepower system or the data logging system. The junction circuit board mayalso connect the end connector wires or other wires to stackers thatallow these signals to be accessed by the modular circuit boards.Through the use of the junction circuit board and the modulararchitecture of the stackable circuits, circuits can be quickly detachedfrom the system, and replaced, if necessary.

The junction circuit board also reduces the amount of cumbersome buttjoints previously necessary in such electrical connections In thisrespect, prior to the junction circuit board and modular architecture,all wiring needed to pass through all circuit boards, a very delicateand tedious process, resulting in reduced usable surface area, decreasedyield or quality of manufacturing and decreased reliability as well aslonger manufacturing times.

In certain embodiments, the junction circuit board also includes ESDprotection (TVS Diode and RC snubber) to protect the sensitive nodes ofthe electronics. The junction circuit board may also be used tofacilitate programming of the any individual circuits attached on thebus by multiplexing the programming lines and keeping the high voltageprogramming line separate.

The supervisor component can relate protocol commands to and from theadditional circuit boards connected to the junction circuit board.

4. System Housing

The housing that contains the MSID for use with downhole electronics maybe disposed inside the tool string. While the housing may be any shapesuitable for disposition of the systems of the invention, in certainembodiments, the housing is circular an conforms to the diameter of thecircular circuit boards described herein. Advantageously, the presentsystems of the present invention, e.g., power systems or data loggingsystems, are positioned in a housing that takes less of the valuablespace in the tool string as compared with existing systems used for thesame purpose. Such additional space efficiency derives from the higherpower and/or signal density achieved with the circuits and architecturethat comprise the MSID; wherein the decreased inner diameter of thehousing affords the ability to reduce the outer diameter housing whileretaining sufficient thickness of the housing material; wherein suchreduction in size of the operable circuits involved significantinventive design of the circuits. However, additional embodiments ofhousing improvements, including increases to modular aspects of thehousing for ease of serviceability and manufacture are shown hereinbelow.

System Components

In one embodiment, the system of the present invention comprises amodular signal interface device (MSID) configured as a component of apower system. In one example, the MSID may comprise various circuits.Non-limiting examples include a junction circuit, at least one sensorcircuit, an ultracapacitor charger circuit, an ultracapacitor managementsystem circuit, a changeover circuit, a state of charge circuit, and anelectronic management system circuit.

In one embodiment, the MSID comprises a junction circuit, anultracapacitor charger circuit, an ultracapacitor management systemcircuit, a changeover circuit, a state of charge circuit, and anelectronic management system circuit.

In one embodiment, the MSID further comprises modular circuit boards. Infurther embodiments the modular circuit boards are circular. In furtherembodiments, the modular circuit boards are stacked. In furtherembodiments, the modular circuit boards are circular and stacked.

In certain embodiments, the power source comprises at least one of awireline power source, a battery, or a generator.

In certain embodiments, the power source comprises at least one battery.In this embodiment, the MSID may further comprise a cross over circuit,particularly when the power source comprises more than battery. Inparticular embodiments, the MSID further comprises a state of chargecircuit board.

In certain embodiments, the power source comprises a wireline, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the power source comprises a generator.

In certain embodiments, the power source comprises a generator, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the circuit boards may be combined to providemulti-functional circuit boards.

In certain embodiments, the MSID comprises a power converter. In furtherembodiments said power converter is a switched-mode power converter. Insome embodiments, said power converter is regulated by way of feedbackcontrol. Examples of power converters include inductor-based converters,for example, buck, boost, buck-boost, cuk, forward, flyback, or variantsor the like as well as inductorless converters such as switchedcapacitor converters.

By using switched mode power conversion, power systems of the presentinvention generally achieve efficiencies greater than 60%, e.g. greaterthan 70%, e.g. greater than 80%, e.g. greater than 90%, e.g. greaterthan 95%.

By using regulated power converters, power systems of the presentinvention afford regulated aspects of voltage, current and/or power. Byusing power converters, power systems of the present invention affordtransformations of power, voltage and/or current.

1. Ultracapacitor Charger (UCC)

In certain embodiments, the MSID comprises a power converter. In furtherembodiments, the power converter is a UCC circuit. The UCC circuitfeatures high temperature operation, e.g., greater than 75 degreesCelsius, e.g., greater than 125 degrees Celsius, e.g., 150 degreesCelsius, adjustable charge current control, redundant over voltageprotection for the capacitor bank, and a wide input/output voltagerange. In certain embodiments, the controller IC uses current moderegulation to mitigate the effect of the art-known right half plane(RHP) zero on output voltage during load transients. In this respect,the UCC circuit of the present invention provides an optimal range ofoperation whereby the converter is charging at a calibrated duty cycleto minimize overall losses, e.g., wherein the bus voltage is optimized.

In certain embodiments, the UCC circuit uses switch mode powerconversion, wherein at low ultracapacitor charge, the IC uses the moreefficient, i.e., less lossy, current mode control, and subsequentlyswitches to voltage control mode at greater levels of ultracapacitorcharge storage where such switching would result in more efficientcharging of the ultracapacitor.

In certain embodiments, the MSID affords input current shaping, e.g., inapplications where continuous and steady current draw from the energysource is desirable or a particular pulsed profile is best. Inparticular embodiments, such current shaping prevents undesirableelectrochemical effects in batteries such as cathode freezeover effectsor passivation effects.

In certain embodiments, the MSID affords input current smoothing, e.g.,in applications where continuous and steady current draw from the energysource is desirable. In particular embodiments, such current smoothingreduces conduction losses in series resistances.

In certain embodiments, wherein the UCC circuit is operating in constantvoltage mode, the UCC is capable of supplying a constant voltage in theevent of a capacitor string disconnection. For example, the UCC cancontinue to source power into the load at a lower level.

In one embodiment, the UCC controller is implemented digitally. Theadvantages of such a system include component reduction andprogrammability. In certain embodiments, the control of the switchnetwork is performed by a microcontroller/microprocessor.

In one embodiment, adjustable current may be established digitally witha Pulse Width Modulated (PWM) control signal created by a supervisor anda low pass filter to produce an analog voltage that the controller ICinterprets as the controller IC does not communicate digitally. Thecontroller IC is configured to regulate output current, e.g., theultracapacitor charge current. Through control of the charge current,the UCC circuit is capable of regulating the voltage on theultracapacitors, e.g. by hysteretic control wherein the voltage is keptwithin a voltage band by on-off control of the IC.

The UCC circuit, in certain embodiments, may be digitally controlled. Infurther embodiments, the UCC circuit is digitally controlled by theelectronics management system (EMS). In further embodiments, the UCCcircuit can enter sleep mode to conserve energy and this aspect may beprovided for by a digital control.

The UCC controller can also be implemented in an analog fashion. In sucha configuration, the feedback control would generally be carried outwith the use of components such as operational amplifiers, resistors,and capacitors. While effective, a minor disadvantage of thisconfiguration is the inherent lack of flexibility controlling chargecurrent and output voltage.

In certain embodiments, the controller integrated circuit (IC) at thecenter of the Ultracapacitor Charger (UCC) is electrically connected bymodular bus stackers to and programmed to communicate with the junctioncircuit, the EMS circuit, cross over circuit, and/or one or more energysources (such as battery, generator, or wireline). The UCC circuit mayalso comprise a resistor network for voltage sampling, a step down powersection (e.g., a Buck converter), a step up power section (e.g., a boostconverter), an inductor current sense resistor required for current modecontrol, and/or a charge current sense resistor required for regulatingthe charge current.

In certain embodiments, a power converter for charging an ultracapacitoris controlled hysteretically. For example, a charging current isregulated by the converter and a feedback control circuit. A voltage ofan ultracapacitor is measured by the power converter or a supervisor orthe like. The power converter may be disabled for instance when avoltage on an ultracapacitor reaches a certain threshold. Alternatively,the charging current may be reduced when the voltage reaches a certainthreshold. In this way, various benefits may be realized. First, avoltage set point and hysteresis band may be set in firmware orsoftware, i.e. digitally, without a redesign of feedback controlcircuitry, e.g. redesign that may otherwise be required for stabilityand dynamics. Thus, the output voltage is easily adjusted by a user orby a controller, e.g. in run-time. Second, whereas an efficiency ofcharging an ultracapacitor will generally be improved by limiting orregulating a charging current, and many loads expect a voltage within arange to operate properly, a controller having a feedback control forregulating a charging current may be used to provide for a voltagechosen to fall within a range to operate a load properly.

2. Cross Over (XO) Circuit

In certain embodiments, the cross over circuit is a peripheral circuitboard that can seamlessly be added into the modular architecture throughstackers electrically connected and controlled by the junction circuitboard to enable the use of multiple power sources. Along with the UCCcircuit, the cross over circuit possesses autonomous capability.

In one embodiment, the cross over circuit can be preprogrammed to switchfrom one power source to another after the initial source has beendepleted.

In another embodiment, the cross over circuit has the ability toparallel two sources together and to either increase the power capableof being delivered to the load, or to extract the very last remainingenergy of the individual power sources where the individual, nearlydepleted sources could not deliver enough power to drive the load alone.

The cross over circuit, in certain embodiments, may be digitallycontrolled by the electronics management system (EMS) and can entersleep mode to conserve energy.

The cross over circuit may comprise a supervisor, and in certainembodiments is electrically connected by the modular bus stackers to,and programmed to communicate with: the junction circuit, the EMScircuit, state-of-charge circuit, and/or one or more energy sources(such as battery, generator, or ultracapacitor string) through thesupervisor of the circuit. The cross over circuit may also comprise acurrent sense resistor; a resistor network for voltage sampling; acurrent sense resistor for state-of-charge measurements; aunidirectional primary disconnect that allows the BUS voltage to bebootstrapped to the primary source, where power is initially processedthrough a low forward voltage diode in parallel with the p-channelMOSFET to reduce dissipation during the bootstrapping operation and oncevoltage is established on the bus, the primary disconnect may be turnedon (the p-channel MOSFET is enhanced) by a resistor-diode network andn-channel MOSFET; a bidirectional secondary disconnect that processespower from the secondary source to the BUS, where the secondarydisconnect, unlike the primary disconnect, can fully disconnect thesecondary source from the BUS; a resistor-diode network for biasing thegate of the p-channel MOSFET, sized to allow for low voltage disconnectoperation (resistor divider) and high voltage disconnect operation(diode clamps the gate voltage to a safe operating voltage); and/or ableed resistor to ensure the n-channel MOSFET is turned off in theabsence of a control signal.

3. State of Charge (SoC) Circuit

In certain embodiments, the SoC circuit serves to provide for anestimate of the remaining and/or used capacity of a given energy source.This circuit can combine measured current, temperature, the time domainshape of the current profile, and can produce a model to determine theremaining runtime for a given energy source.

Measurement of current is an important factor in determining the servicetime of an energy source, in particular, a battery. As such, in certainembodiments, current may be measured using an off-the-shelf IC thatserves as a transconductance amplifier. In certain embodiments, currentmay be measured using Hall Effect sensors/magnetometers, inductivesensors, magnetic sensors, or high-side or low side current senseresistors

Temperature may be measured using a resistance temperature detector(RTD), a resistor with a large temperature coefficient, (temperaturedependent resistance). The resistance is read through the use of aresistor divider tied to the output pin of a microcontroller. Theresistor divider is pulled up to 5V when a measurement is to be taken.Turning the resistor divider on and off saves power and reducesself-heating in the resistance. Other methods of measuring temperatureinclude use of bi-metallic junctions, i.e. thermocouples, or otherdevices having a known temperature coefficient transistor basedcircuits, or infrared detection devices.

These measurements can be used as inputs to a given model describing thebehavior of a given energy source over time. For instance, greatvariations in battery current have been shown to reduce the ratedcapacity of a Li—SOCL2 battery. For this battery chemistry, knowledge ofthe current profile would be useful in determining the remainingcapacity of the battery.

The state of charge circuit may comprise a supervisor, and in certainembodiments is electrically connected by the modular bus stackers to,and programmed to communicate with: the junction circuit, the EMScircuit, the cross over circuit, and/or one or more energy sources (suchas battery or ultracapacitor string) through the supervisor of thecircuit. The state of charge circuit may also comprise an external commbus implemented with pull up resistors; a voltage regulator used toestablish an appropriate voltage for the supervisor and other digitalelectronics; a current sense circuit; unidirectional load disconnect,wherein a p-channel MOSFET is enhanced via a control signal to thepulldown n-channel MOSFET and a resistor divider ratio is chosen toallow proper biasing of the p-channel MOSFET at low voltage levels,while the zener diode serves to clamp the maximum source-gate voltageacross the MOSFET; and/or resistor divider networks and ADC buffer capnecessary for analog voltage reading

4. Ultracapacitor Management System (UMS) Circuit

In certain embodiments, the MSID comprises an ultracapacitor managementsystem (UMS) circuit. The ultracapacitor management system circuit hasthe primary purpose of maintaining individual cell health throughoutoperation. The UMS circuit may measure individual cell voltages orvoltages of a subset of cells within a string and their charge/dischargerates. The UMS circuit supervisor uses these parameters in order todetermine cell health which may be communicated to the electronicsmanagement system (EMS) circuit to be included in optimizationalgorithms and data logs.

Additionally, in certain embodiments, the UMS circuit is responsible forcell balancing and bypassing. Cell balancing prevents ultracapacitorsfrom becoming overcharged and damaged during operation. Cell bypassingdiverts charge and discharge current around an individual cell. Cellbypassing is therefore used to preserve efficient operation in the eventthat a cell is severely damaged or exhibiting unusually high equivalentseries resistance (ESR).

The UMS circuit is capable of determining individual cell health throughfrequent cell voltage measurements and communication of the chargecurrent with the EMS. The cell health information may be relayed to theEMS circuit over the modular communication bus, e.g., through themodular bus stackers. The cell health information can then be used bythe EMS circuit to alter system behavior. For example, consider that theEMS circuit is supporting high output power to a load by regulating to ahigh output capacitor voltage. If however, the UMS circuit reports thatone or multiple ultracapacitors are damaged, the EMS can choose toregulate to a lower output capacitor voltage. The lower output voltagereduces output power capabilities but helps preserve ultracapacitorhealth.

As such, in one embodiment, the UMS circuit offers a convenient methodto independently control cell voltage levels while monitoring individualand ultracapacitor string cell health.

In certain embodiments, as shown in FIG. 33, the supervisor of the UMScircuit may communicate to the UMS core via an internal circuitcommunication bus. In this example, data and command signals aretransferred over the internal communication bus. The supervisor controlsthe UMS core to measure each cell voltage. Depending on the state ofcharge, the supervisor commands the UMS core to balance each cell. Inparticular embodiments, the balance time and frequency is controlled viathe supervisor to optimize cell health and to minimize heat increasesthat may arise during balancing. Cell health may be monitored by thesupervisor and communicated by the supervisor to the EMS circuit via themodular bus. Additionally, in certain embodiments, through the use ofexternal devices, e.g. MOSFETs, the supervisor can decide to bypass agiven cell.

The UMS Core has circuitry that enables measuring the voltage ofindividual cells. Additionally, the UMS core is capable of removingcharge from individual cells to reduce the cell voltage. In oneembodiment, the UMS core balances individual cells by dissipating theexcess energy through a passive component, such as a resistance. Inanother embodiment, charge can be removed from one cell with highvoltage and transferred to another cell with low voltage. The transferof charge can be accomplished through the use of external capacitors orinductors to store and release excess charge.

In certain embodiments, since cell balancing and monitoring does nothave to occur continuously, i.e., at all times, the UMS circuit mayenter a low power sleep state. For instance, an EMS circuit may controlthe UMS circuit via the modular communication bus so that: (1) when notin use, the UMS circuit can go to a low power consumption mode ofoperation and (2) when called upon, the EMS circuit can initiate cellmonitoring and balancing via the UMS supervisor.

In certain embodiments, the modular bus enables bi-directionalcommunication between the UMS circuit supervisor, EMS circuit, and othersupervisor nodes on the communication bus. As shown in FIG. 33, power tothe UMS circuit supervisor may also be provided through the modular bus.

In certain applications, balancing circuitry may automatically balance acell when the cell voltage exceeds a set voltage. This behavior affordsthe capability to perform real-time adjustments to the ultracapacitorstring voltage. An UMS circuit may be configured to communicate on themodular bus thereby enabling real-time updates to cell balancingbehavior. In addition, communication on the modular bus enables data tobe stored external to the UMS circuitry. This modularity enables the UMScircuit to have a wide range of applications.

In certain embodiments, the supervisor and modular bus allow for changesin the ultracapacitors and system requirements, such as loggingresolution and lifetime, without requiring extensive revisions to UMScircuitry.

In certain embodiments, the cell health information can be storedlocally on the UMS circuit or stored by the EMS after transmission overthe modular bus. The cell information can be useful in determiningwhether a bank of ultracapacitors needs to be replaced after usage orwhether service is required on individual cells.

In certain embodiments, when a cell experiences a high voltage, the UMScircuit is capable of discharging that cell to a lower voltage. Bydischarging the cell to a lower voltage, cell lifetime is improved.Maintaining balanced cell voltage over the entire string improvesoptimizes lifetime of the capacitor string.

In certain cases, discharging a cell produces excess heat that candamage surrounding electronics. Furthermore, it is often advantageous tocontrol the discharge current from a cell in order to prevent damage tothe cell or excess thermal losses. As such, in certain embodiments, theUMS circuit is capable of controlling the discharge current profile, bydistributing discharge currents across a widely separated circuit area,enabling improved thermal management and cell health. For example, heatcaused by a discharging event is often localized to a section of the UMScircuit. If multiple cells need to be balanced, it is advantageous inorder to reduce temperature increases not to balance cells that wouldcause temperature increases in adjacent location on the UMS circuit.Therefore, the UMS circuit manages temperature increases by selectingwhich cells to balance based on their spatial location on the UMScircuit. These features may be managed my a supervisor and additionallymay be managed by an EMS and/or a combination of the above.

In certain embodiments, the UMS circuit also manages temperatureincreases during balances by controlling the time of discharge. Forexample, instead of constantly discharging an ultracapacitor until thedesired cell voltage is met, the supervisor chooses to start and stopcharging periodically. By increasing the duty cycle between dischargeevents, temperature increases caused by cell discharge current can bemitigated.

In certain embodiments, a damaged cell may exhibit a decreasedcapacitance compared to surrounding cells. In this case, the cell willexhibit higher charge and discharge rates. Normal balancing operationswill mitigate any damage to the cell in this case. Similarly, in certainembodiments, a cell may exhibit increased leakage current, causing aconstantly dropping cell voltage. A decreased voltage on a cell willrequire other cells to maintain a higher average voltage. Again, normalbalancing operations will mitigate damage to cells in this case.

In certain embodiments, a cell may be damaged to the point where itexhibits very high ESR, degrading the power handling of the entirecapacitor string. In these cases, typical balancing operations will notfix the problem. At this juncture, the UMS circuit can choose to bypassany given cell. Cell bypassing may be achieved via nonlinear devicessuch as external diodes that bypass charge and discharge current, suchthat every other cell must store a higher average voltage. However,power handling capability of string is maintained.

In certain embodiments, where there are multiple batteries and/orultracapacitors connected in series or parallel series, it is importantto both monitor and balance the state of charge of individual cells. TheUMS circuit comprises of necessary circuitry to monitor and balance astring of ultracapacitors while including additional functionality toimprove efficiency, system health, and thermal management.

The UMS circuit in certain embodiments comprises a supervisor, iselectrically connected by the modular bus stackers to, and programmed tocommunicate with: the junction circuit, the EMS circuit, the state ofcharge circuit, the cross over circuit, or other circuits in the MSID,and/or one or more energy sources (such as a battery, wireline orgenerator). The UMS circuit may also comprise an integrated circuit (IC)or controller for performing the functions of the UMS, switch devicessuch as transistors or diodes, and various ancillary components. The ICmay be selected from off-the-shelf monolithic control IC's.

5. Electronics Management System (EMS) Circuit

In certain embodiments, the MSID comprises an EMS circuit. The EMScircuit is a multifunctional device capable of one or more of thefollowing: collecting and logging data of system performance andenvironment conditions; managing other circuits; and communicating toexternal systems for programming and data transmission.

In certain embodiments, the EMS circuit hardware is tightly integratedwith surrounding hardware, enabling the control and monitoring of totalsystem behavior. The hardware may be complemented by intelligentfirmware that manages the operation of several other microcontrollers,using external sensors and communication between the microprocessors tointelligently optimize system performance. The effect is an extremelyversatile and capable system, one that can adapt in real-time to changesin the environment and requirements.

In certain embodiments, the EMS circuit collects and logs data of systemperformance and environmental conditions. The EMS circuit, e.g., via theEMS circuit supervisor, is responsible for recording sensor datadirectly from external sensors and through communication over themodular bus from other circuits. This data may be used to evaluatesystem performance for optimization. In general, significant events mayalso be logged for later evaluation.

In certain embodiments, the EMS circuit manages surrounding circuits foroptimal system performance. For example, the EMS circuit may control theUCC circuit charging current. The charging current may be selected basedon the data collected throughout the system through sensors andcommunication with the circuits. The EMS circuit can also put variouscircuit components into a low power sleep state to conserve power whenpossible.

In certain embodiments, the EMS circuit communicates to external systemsfor programming and/or data transmission. The external communication buson the EMS circuit enables communication to outside hardware andsoftware. This connection enables the EMS circuit to be reprogrammedwhile disposed in the system. The EMS can then reprogram othersupervisors or direct other supervisors on their operation, effectivelyreprogramming the entire system. The external communication bus is alsoused to transmit data logs from internal memory to external software. Inthis way, data can be collected during operation and analyzedpost-operation by external equipment, e.g., an external PC.

In one embodiment, the Electronics Management System (EMS) circuitserves to collect information from available supervisors and sensors anddependently control system behavior. The EMS also provides an interfaceto external electronics, such as PC software or firmware programmers.Through the external communication bus, it is possible to program theEMS circuit core, e.g., the EMS circuit supervisor, and consequently allother supervisors connected to the EMS circuit.

The EMS circuit core may be comprised of one or more digital circuits,e.g., microcontrollers, microprocessor, or field-programmable gate array(FPGA) units. In certain embodiments, the EMS circuit core is connectedto a load connect/disconnect circuit that allows the ultracapacitorstring to be connected or disconnected to an external load. Thecapacitor string may be disconnected from the load if, for example, thecapacitor string voltage is too low or too high for the particular load.During normal run-time operation, the load is connected to theultracapacitors through a load driver circuit.

In certain embodiments, the EMS circuit is connected to additionalsensors that are not interfaced to other supervisors. These sensors mayinclude one or more of the group consisting of a temperature sensor, aload current sensor, an input battery current sensor, an input voltagesensor, and a capacitor string voltage sensor.

Through the modular bus, the EMS circuit may be connected to othercircuits. The communication bus may comprise data line, a clock line,and an enable line. In some embodiments, supervisors interface to thedata, clock, and enable lines. Furthermore, each supervisor can beprescribed an identification address.

In one embodiment, to communicate over the internal communication bus,the EMS circuit, as shown in FIG. 35, activates the enable line andsends over the data and clock lines the identification address of thetarget supervisor followed by the desired data command instructions.When the supervisors see the enable line activated, each supervisor willlisten for its prescribed identification address. If a supervisor readsits identification address, it will continue to listen to the EMScircuit message and respond accordingly. In this way, communication isachieved between the EMS circuit supervisor and all other supervisors.

In certain embodiments, the EMS circuit interfaces with the UCC circuitand controls the UCC circuit charge current. The charge current iscontrolled to regulate the output ultracapacitor voltage. Feedbackcontrol and/or heuristic techniques are used to ensure safe andefficient operation of the electronics, ultracapacitors, and inputbattery stack.

In certain embodiments, the EMS circuit interfaces with the cross overcircuit to record and potentially control the battery connection state.The state of the cross over circuit and crossover events may be loggedvia the EMS and internal/external memory.

In certain embodiments, the EMS circuit interfaces with the UMS circuitin order to monitor and log cell health and/or discharge events.

In certain embodiments, the EMS circuit is capable of bringingsupervisors into a low power state to decrease power consumption andoptimize run-time behavior.

As described herein, the EMS circuit has a unique hardware structurethat allows communication to and from a large variety of sensors,lending itself to a variety of advantages that generally serve tooptimize one or more performance parameters, e.g., efficiency, poweroutput, battery lifetime, or capacitor lifetime.

The EMS circuit in certain embodiments comprises a supervisor, iselectrically connected by the modular bus stackers, and programmed tocommunicate with: the junction circuit, the UMS circuit, the state ofcharge circuit, the cross over circuit, and/or one or more energysources (such as battery or ultracapacitor string) through thesupervisor of the circuit. The EMS circuit may also comprise at leastone digital controller, e.g. a microcontroller, a microprocessor, or anFPGA, and various ancillary components.

6. Load Driver Circuit

In certain embodiments, an MSID may comprise a load driver circuit.

For embodiments of the present invention wherein the power system mayprovide power for relatively high energy applications (e.g., driving asolenoid based or motor-based mud pulser, an EM transmitter, or a motordrive for extended periods of time), the MSID may comprise a load drivercircuit. The load driver circuit, in certain embodiments, acts as apower converter that may provide an aspect of regulation, for instancevoltage regulation of the output of a power system despite anotherwidely varying voltage aspect. For example, when a power source isintermittent, e.g. it provides power for several minutes and then ceasesto provide power for several minutes, a power system may be required toprovide power to a load when the power source is not providing power. Inthis example, a HTRES may provide the stored energy for the supply ofpower during the period when the power source is not providing power. Ifthe HTRES is an capacitor, for instance an ultracapacitor, a limitedenergy capacity of said HTRES may lead to a widely varying voltage ofsaid HTRES during a period when the power system is providing power to aload, but the power source is not providing power. A load driver may beemployed in this example to provide for a regulated load voltage despitethe widely varying HTRES voltage. The load driver may function as apower converter so that it processes the power drawn from said HTRES anddelivered to said load and so that it also incorporates said regulationaspects, i.e. a regulated power converter, in this example, an outputvoltage regulated power converter. Generally a regulation aspect isenabled by art-known feedback regulation techniques.

In certain embodiments, the controller integrated circuit (IC) at thecenter of the load driver circuit is electrically connected by modularbus stackers to and programmed to communicate with the remainder of theMSID. For example, in certain embodiments, the remainder of the MSID maycomprise various circuits. Non-limiting examples include a junctioncircuit, at least one sensor circuit, an ultracapacitor charger circuit,an ultracapacitor management system circuit, a changeover circuit, astate of charge circuit, and an electronic management system circuit.

In one embodiment, the MSID further comprises modular circuit boards. Infurther embodiments the modular circuit boards are circular. In furtherembodiments, the modular circuit boards are stacked. In furtherembodiments, the modular circuit boards are circular and stacked.

In certain embodiments, the power source comprises at least one of awireline power source, a battery, or a generator.

In certain embodiments, the power source comprises at least one battery.In this embodiment, the MSID may further comprise a cross over circuit,particularly when the power source comprises more than battery. Inparticular embodiments, the MSID further comprises a state of chargecircuit board.

In certain embodiments, the power source comprises a wireline, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the power source comprises a generator.

In certain embodiments, the power source comprises a generator, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the circuit boards may be combined to providemulti-functional circuit boards.

The load driver circuit features high temperature operation, e.g.,greater than 75 degrees Celsius e.g., greater than 125 degrees Celsius,e.g., 150 degrees Celsius, and may comprise any of an adjustable chargecurrent control, redundant over voltage protection for the capacitorbank, and a wide input/output voltage range, and voltage moderegulation.

In certain embodiments, the load driver charges a capacitor, e.g. anultracapacitor. In these embodiments, an adjustable current may beestablished digitally with a Pulse Width Modulated (PWM) control signalcreated by a supervisor and a low pass filter to produce an analogvoltage that the controller IC interprets as the controller IC does notcommunicate digitally. The controller IC is configured to regulateoutput current, e.g., the ultracapacitor charge current. Through controlof the charge current, the UCC circuit is capable of regulating thevoltage on the ultracapacitors, e.g. by hysteretic control wherein thevoltage is kept within a voltage band by on-off control of the IC.

The load driver circuit, in certain embodiments, may be digitallycontrolled. In further embodiments, the load driver circuit is digitallycontrolled by the electronics management system (EMS). In furtherembodiments, the load driver circuit can enter sleep mode to conserveenergy and this aspect may be provided for by a digital control.

The load driver controller can also be implemented in an analog fashion.In such a configuration, the feedback control would generally be carriedout with the use of components such as operational amplifiers,resistors, and capacitors. While effective, a minor disadvantage of thisconfiguration is the inherent lack of flexibility controlling chargecurrent and output voltage.

In certain embodiments, the controller integrated circuit (IC) at thecenter of the load driver circuit is electrically connected by modularbus stackers to and programmed to communicate with the junction circuit,the EMS circuit, cross over circuit, and/or one or more energy sources(such as battery, generator, or wireline). The load driver circuit mayalso comprise a resistor network for voltage sampling, a step down powersection (e.g., a Buck converter), a step up power section (e.g., a boostconverter), an inductor current sense resistor required for current modecontrol, and/or a charge current sense resistor required for regulatingthe charge current.

In one embodiment, the load driver circuit controller is implementeddigitally. The advantages of such a system include component reductionand programmability. In certain embodiments, the control of the switchnetwork is performed by a microcontroller/microprocessor.

7. Amplifier Circuit

Processing of high power levels often requires very efficient powerelectronics. Inefficiencies in power electronics result in temperatureincreases that can damage electronics and ultracapacitors. Therefore, inorder to process significant power, high efficiency power electronicsare often required. The class D topology, is art-recognized, as designedfor high efficiency operation. High efficiency is achieved by runningthe output transistors in either a fully enhanced or off state. Whenfully enhanced, the MOSFETs can ideally be considered a short with nointernal resistance. In this state, there is high current but no voltagedrop over the output transistors, resulting in no power loss. In theiroff state, the MOSFETs ideally block all current at high voltage,resulting in no power loss. In present embodiment, the MOSFETs are notconsidered ideal switches, but rather power losses are mitigated throughproperly chosen switching frequencies and low loss components. The aboveessentially describes the basic concepts associated with art-recognizedswitch-mode operation. When switched-mode operation is applied toamplifiers, those amplifiers are often termed class-D amplifiers.

In certain embodiments, a class D Amplifier enables significantly higherpower capabilities when compared to existing solutions. In a particularembodiment, the amplifier comprises six main components connected in aClass D full bridge switching amplifier configuration, i.e., alsotogether referred to as a Class D amplifier: (1) High voltage capacitorrail; (2) Modulator; (3) device drivers; (4) Switching Section; (5)Signal low pass filters; and (6) Load impedance.

High Voltage Capacitor Rail

The high voltage capacitor rail supplies a positive rail voltage to theoutput transistors. In order to deliver significant power to the load,it is important that the high voltage capacitor rail maintain lowimpedance, minimizing power losses under heavy loads.

Modulator

The modulator has the function of modulating the signal provided to theload. The modulator may function in a number of ways. The modulator maymodulate a number of quantities, e.g. power, voltage, current,frequency, and phase.

An example open-loop method for modulating amplitude of the voltagepresented to the load includes providing a time-varying analog signal asa time-varying reference input to a pulse-width modulator circuit, e.g.a comparator having two inputs one being said reference, the other beinga triangle wave signal oscillating at the desired switching stageswitching frequency, the pulse-width modulator circuit providing thepulse width modulated gate driver control signal. By time-varying thereference voltage input to the pulse width modulator circuit, the dutyratio of the gate driver control signal is also varied, the duty cycleof said control signal in turn may control the instantaneous voltagepresented to the load.

An example closed-loop method for modulating amplitude of the voltagepresented to the load includes providing a time-varying analog signal asa time-varying reference input to a feedback control circuit, thefeedback control circuit configured to regulate the voltage presented tothe load by various methods known in the art. Generally, the feedbackcircuit comprises measurement aspects of feedback signals, an erroramplifier, a dynamic compensator, a pulse width modulator, a gatedriver, which may comprise a dead-time circuit. The dynamic compensatoris generally designed to achieve a combination of closed-loop stabilityand closed-loop dynamics.

Device Drivers

The device drivers generally provide current or voltage amplification,voltage level shifting, device protection and in some cases signal deadtime generation in order to properly drive the transistor inputs.Generally device drivers convert a low level control signal to a signalappropriate for controlling a device. Example devices include bipolarjunction transistors, MOSFETs, JFETs, Super junction transistors orMOSFETs, silicon-controlled rectifiers, insulated gate bipolartransistors and the like. Gate drivers may be provided as discreteimplementations or as off-the-shelf or monolithic integrated circuits.

Switching Section

The switching section comprising generally comprises output transistorsswitches processes input power to provide a transformed power to theload. An example switching section is configured in a full bridgeconfiguration such that the two of the transistors are on at any giventime. In one state, two transistors are on, providing a current flowthrough the load in one direction. In the other state, the other twotransistors are on, providing a current flow through the load in theopposite direction.

Filtering

Each of the transistors are switched a frequency well above thebandwidth of the reference signal. In order to accurately recreate anamplified version of the reference signal over the load, low passfilters are used to filter out the high frequency switching signal,ideally leaving only the low frequency reference signal transmittedthrough the load. The low pass filters are reactive components toprevent losses that would other occur over resistance components.Filtering between the switching section and the load should pass thefrequency content desired in the modulated signal to the load.Meanwhile, the filtering should be band-limited enough to rejectunwanted frequency content.

Load

In present invention, the load impedance represents the medium overwhich the telemetry signal is being transmitted. Load impedancescommonly contain high order behavior that determines how the signal willpropagate through space. Simple models, however, are represented by apower resistor.

While switching amplifiers may introduce switching artifacts in theoutput signal, in certain embodiments, these artifacts are minimizedthrough the use of properly selected switching frequencies, and/orwell-designed filtering. In a particular embodiment, the output filterpreserves signal integrity by severely attenuating switching artifactswhile preserving the information contained in the reference signal. Theoutput filter may also contribute minimal power loss through having verylow resistance components

8. Sensorless Motor Drive Circuit

In harsh environment applications, brushless DC (BLDC) motors have beenutilized for a variety of applications, for example, to operate mudpulsers used for downhole Measurement While Drilling (MWD), i.e.,providing mud pulse telemetry. However, conventional BLDC motors ofteninclude and rely on rotor position sensors. A common example of a rotorposition sensor is a Hall effect sensor. Under harsh conditions, i.e.high temperature, high shock and high vibration, e.g., temperaturesgreater than 70 degrees Celsius, continuous vibration greater than 2 Grms and shock greater than 20 G, rotor position sensors and inparticular, Hall Effect sensors of a sensored motor present reliabilitylimitations and are often damaged or fail. In order to address theseissues, the present invention provides a sensorless BLDC motor drivethat may operate either a sensorless brushless DC (BLDC) motor or aretro-fitted sensored BLDC (e.g., one with either working or failedsensors) by using electronic commutation of a 3-phase BLDC (i.e., “wye”)motor, wherein the BLDC motor drive is configured to operate the BLDCmotor according to a sequential commutation algorithm.

Coupling the motor drive disclosed herein with a power system alsodescribed herein can lead to a number of benefits. For example, a powersystem for high power applications coupled to the motor drive may beused to drive a mud pulser harder, which translates to sharper pressurepulses and potentially faster data rates for transmission to thesurface, e.g., up to twice the data rates while maintaining battery lifeand without compromising signal integrity, e.g., using mud pulsetelemetry.

The configuration eliminates the use or need of Hall Effect sensors indownhole brushless DC motor drives; where the BLDC motor drive describedherein enables the use of a reliable brushless DC motor in a downholeenvironment. Moreover, at least five required wires (5V, GND, H1, H2,H3) present on a conventional sensored BLDC motor can be eliminated,thereby increasing reliability, and reducing complexity.

As such, another power system embodiment of the invention provides apower system adapted for buffering the power from a power sourcecomprising: a high temperature rechargeable energy storage (HTRES),e.g., an ultracapacitor string organized in a space efficientorientation as described herein, an optional load driver circuit, asensorless brushless DC motor drive circuit, and a controller forcontrolling at least one of charging and discharging of the energystorage, wherein the system is adapted for operation in a temperaturerange of between about seventy five degrees Celsius to about two hundredand ten degrees Celsius; and wherein the load comprises a brushless DCmotor, e.g., a sensorless BLDC motor. In certain embodiments, thecontroller is an MSID of the present invention.

Accordingly, in another embodiment, the invention is directed to asensorless brushless DC motor system comprised of a power source a hightemperature rechargeable energy storage (HTRES), e.g., an ultracapacitorstring (e.g., of 1-100 ultracapacitor cells) organized in a spaceefficient orientation as described herein, an optional load drivercircuit, a sensorless brushless DC motor drive circuit, and a controllerfor controlling at least one of charging and discharging of the energystorage, wherein the system is adapted for operation in a temperaturerange of between about seventy five degrees Celsius to about two hundredand ten degrees Celsius; and wherein the load comprises a brushless DCmotor. In certain embodiments, the controller is an MSID of the presentinvention.

Moreover, in certain embodiments, the sensorless brushless DC motordrive is configured to receive the filtered motor terminal voltages andcompare them pair-wise using comparators whose outputs are utilized togenerate commutation control signals. For example, when the positiveinput of the comparator goes below the negative input, the output of thecomparator saturates to the negative power supply rail and to thepositive power supply rail if the inputs are interchanged. The state ofthe rotor position can be determined from the state of the outputs ofthe outputs of the comparators.

A sensorless brushless DC motor, e.g., a 3-phase motor, may be driven sothat its phases are energized based on the position of the rotor. Ascurrent passes through a stator coil, magnetic poles are created withpolarity according to right hand thumb rule. As shown in FIG. 36, whentwo phases are energized at the same time, the current flowing in thetwo phases are in opposite directions to each other with respect to thesource. Energized poles formed by the stator coils attract the rotorpoles, and as the rotor is approaching those poles the correspondingstator coils may be de-energized and the next pair of coils energized tocreate rotor motion. When the rotor rotates, the back EMF of theinactive phase forces the comparator outputs to change state thattriggers the controller to match the current state in the look up tableand then move to the next state.

In certain embodiments, when the motor drive is powered on, analgorithm, such as that shown in FIG. 37, in the sensorless BLDC motordrive identifies the state of the rotor by rotating to a known position.As the rotor moves toward the new position, the movement of thepermanent magnets relative to the stator windings generates sufficientback EMF such that the outputs of the comparators become valid. Havingvalid comparator outputs, the system has valid commutation controlsignals and can therefore determine both commutation timing and the nextenergizing step. From this point, the sensorless BLDC is able tocontinue sensorless operation, whereby the controller is able to look upthe next state, for example, in a stored look-up table like the oneshown below. Note that the next energizing state depends on the desiredrotational direction (clockwise or counterclockwise). Performance iscomparable to that for a sensored method in that commutation signalsbecome available immediately after the motor drive is powered on. Thiseliminates the need for start-up procedures that run the motor insynchronous mode to reach speeds when back EMF can be detected.

TABLE 1 Look Up Table Counter Clockwise Clockwise Current EnergizingNext Energizing Next Energizing State Step Step Step 101 AB AC CB 001 ACBC AB 011 BC BA AC 010 BA CA BC 110 CA CB BA 100 CB AB CA 000 XX AB AB111 XX AB AB

TABLE 2 Definition of State Bits referenced in the Look up Table: State= (bit 2, bit 1, bit 0) A_(avg) ≥ C_(avg) bit 2 B_(avg) ≥ A_(avg) bit 1C_(avg) ≥ B_(avg) bit 0

Accordingly, in one embodiment, the invention provides a method ofoperating a sensorless brushless DC (BLDC) motor, e.g., a 3 phase BLDCmotor, comprising a sensorless BLDC motor drive control circuit, arotor, a stator coil, and three comparator outputs of the stator coil,wherein the steps of the method comprise rotating the rotor to align therotor to one of a set of known states of excitation, which generatescontrol signals at the comparators output; passing current through thestator coil such that only two comparator outputs are energized at thesame time creating two phases directed in opposite directions; detectingsufficient back EMF to generate valid commutation control signals todetermine both commutation timing and the next energizing step accordingto the known states of excitation; and performing said next energizingstep according to the known states of excitation, such that rotor motionis produced in a single direction.

In a certain embodiment, the known state of excitation is determined bycomparison to a predefined standard stored in memory, e.g., locally orremotely, electrically coupled to the sensorless BLDC motor drivecontrol circuit. In certain embodiments, the known states of excitationare as provided in the Look-up Table.

In certain embodiments, the rotor is moved in one direction using thefollowing energizing scheme:

-   -   Step 1: First output comparator (A) is driven Positive, Third        output comparator (C) is driven negative and Second output        comparator (B) is not driven;    -   Step 2: First output comparator (A) is driven Positive, Second        output comparator (B) is driven negative and Third output        comparator (C) is not driven;    -   Step 3: Third output comparator (C) is driven Positive, Second        output comparator (B) is driven negative and First output        comparator (A) is not driven;    -   Step 4: Third output comparator (C) is driven Positive, First        output comparator (A) is driven negative and Second output        comparator (B) is not driven;    -   Step 5: Second output comparator (B) is driven Positive, First        output comparator (A) is driven negative and Third output        comparator (C) is not driven;    -   Step 6: Second output comparator (B) is driven Positive, Third        output comparator (C) is driven negative and First output        comparator (A) is not driven;

In another embodiment, the invention provides a sensorless brushless DC(BLDC) motor drive circuit comprising a machine-readable medium havinginstructions stored thereon for execution by a processor to perform amethod comprising operating a sensorless brushless DC (BLDC) motor,e.g., a 3 phase BLDC motor, comprising a sensorless BLDC motor drivecontrol circuit, a rotor, a stator coil, and three comparator outputs ofthe stator coil, wherein the steps of the method comprise rotating therotor to align the rotor to one of a set of known states of excitation,which generates control signals at the comparators output; passingcurrent through the stator coil such that only two comparator outputsare energized at the same time creating two phases directed in oppositedirections; detecting sufficient back EMF to generate valid commutationcontrol signals to determine both commutation timing and the nextenergizing step according to the known states of excitation; andperforming said next energizing step according to the known states ofexcitation, such that rotor motion is produced in a single direction.

In contrast to sensored BLDC motors and other sensorless operationmethods, which have compromised performance at low speeds and start-up,the sensorless BLDC motor, as actuated by the BLDC motor drive of thepresent invention, affords the same torque even at the start-up and therotor picks up the speed almost immediately.

In contrast to sensored BLDC motors and other sensorless operationmethods, the bi-directional rotation of the sensorless BLDC motor, asactuated by the BLDC motor drive of the present invention, is immediate;which makes it suitable as an MWD tool, where opening and closing of thepressure valve is required.

The present invention, which utilizes only three comparators providesfor greater ease of implementation, manufacture, and serviceability ascompared with the conventional sensored motor drives currently in use.

The sensorless brushless motor drive, and the associated motor may beused in all applications where BLDC motors are being used, including,but not limited to Automation, Automotive, Appliances, Medical,Aerospace and military applications.

Fabrication of the Systems of the Present Invention

1. Ultracapacitor String

In certain embodiments of the present invention, the HTRES comprises anultracapacitor string comprised of two or more ultracapacitor cellsorganized in a space efficient orientation, e.g., 1-100 ultracapacitorcells. The ultracapacitors of the present invention may comprise anultracapacitor pack wherein the capacitor assembly, e.g., theultracapacitor string, allows for more cells to be used in a smallerlength of housing. In addition, it leaves room for electrical wires torun along the sides of the pack safely with room for potting to securethem in place.

In another embodiment, and as exemplified in FIG. 30, the inventioncomprises a 3 strand pack assembly of ultracapacitors, e.g., which makesthe system easier to assemble because it is easier to weld togethercells in a smaller group of cells then to weld one long strand of cells.In certain embodiments, an insulation technique, described herein,provides security from short circuit failures and keeps the system rigidin its structure. In particular embodiments, the potting secures thebalancing and system wires in place and protects from unwanted failures,e.g., which is beneficial because more cells can now be fit in the samesize ID housing tube (e.g., going from D sized form factor to AA) but ina significantly shorter housing tube.

In one embodiment, the invention provides an ultracapacitor stringprepared by connecting ultracapacitors in series to be used in thesystems of the invention. In certain embodiments, the cells (e.g., 12 ormore) may be insulated with tape, heat shrink, washers, potting compoundand/or spacers.

In one embodiment, the cell form factor is AA (^(˜)0.53″ in diameter) inwhich 3 strands of equal number of cells are used to minimize the lengthof the capacitor section. In another embodiment, D cells (^(˜1.25)″ indiameter) are used, but are connected in one long strand instead ofthree shorter strands. The insulation and assembly differs slightly fordifferent form factors.

In certain embodiments, the ultracapacitor assembly may also includecapacitor balancing wires and system wires. The AA pack allows thebalancing wires to be safely wired to each cell and protected by pottingand heat shrink. In certain embodiments, heat shrink is applied aroundeach strand, balancing wires and strand, and/or the entire pack of 3strands of cells. In certain embodiments, potting may then used betweeneach pack of cells inside the heat shrink and between the cells. Inparticular embodiments, the balancing wires may be positioned in betweenthe void spaces of the AA strands and are encapsulated in the potting.In a specific embodiment, the system wires run along the void spacesbetween the capacitor strands and do not increase the outermost diameterof the capacitor pack.

In certain embodiments, each cell is insulated with different layers ofprotection. In certain embodiments, a layer of high temperatureinsulation tape, such as Kapton tape, may be placed on the top of eachcell with the glass to metal seal, so only the pin (positive terminal)is exposed. In certain embodiments, another piece of high temperatureinsulation tape may be wrapped around the top side edge of the can andfolded back onto the top face of the can to hold down the first piece oftape. In a particular embodiment, a high temperature spacer disk (suchas Teflon) with the same OD as the can may be positioned around theglass to metal seal pin so only the pin is exposed. In a specificembodiment, he disk sits above the top height of the pin so that whenconnected in series the cans do not press down onto the glass to metalwhen stressed but rather on the spacer.

In certain embodiments, as shown in FIG. 29, the capacitors may beconnected in series using a nickel or similar tab 202. In certainembodiments, the tab may be welded (resistance or laser) to the positiveterminal (usually glass to metal seal pin) of the each capacitor. Incertain embodiments, the tab is run through the center of the spacerdisk. The tab may be insulated with high temperature tape or hightemperature heat shrink except for where it is welded to the positiveterminal and the negative terminal of the next can. The tab may be runflat across the spacer disk 203 and then welded to the bottom of thenext can (negative terminal). In certain embodiments, the tab is thenfolded back so the one can is sitting on the spacer of the next and arein the same line. For D sized cells this is continued until all arewelded together in one string. For AA cells, as shown in FIG. 30, thereare 3 strands with the same number of cells in each. For example, if 12cells are needed for one system, 3 strands of 4 would be weldedtogether. In a particular embodiment, after welding each strand togetherthey are heat shrunk to stabilize the cells and secure the insulationand tabs.

In certain embodiments, the cell balancing wires may be attached byremoving a piece of the heat shrink on each cell and welding thebalancing wire to the side of the can. In certain embodiments, afterwelding the balancing wires, a strip of heat shrink tubing is put aroundthe weld to help secure and protect the wire to the can. The balancingwires may be attached to each can so that they all run along the sameside of the can. In a particular embodiment, tape is used to hold thewire in place after welding, and an additional layer of heat shrink canbe used to keep all the wires in place and on the same side of thestrand of cells. In this embodiment, an added benefit results fromputting the three strands together in that the balancing wires can runin between the extra spaces between the cells of different strands anddo not increase the pack diameter.

In certain embodiments, the three strands of cells are assembled to keepthem all in series. For example, when using 12 AA cells there will be 3strands of 4 cells each. One strand will have the positive terminalwhich will connect to the electronic system. The final negative tab ofstrand one will connect to the positive terminal of strand two, whichwill be in an opposite direction of strand one and the same will go forstrand 3 so that all cells are connected positive to negative. Incertain embodiments, all of the balancing wires are connected so theyall come out the same end of the capacitor pack to make assembly easier.After welding together all 3 strands of cells a final layer of heatshrink may be used to keep all cells together in one rigid body. Inbetween each cell strand, as well as slightly above the top and bottomof the pack, potting may be used to further protect the cell.

On the outside of the final heat shrink there are a number of systemwires that run from end to end. In certain embodiments that use the AAassembly method, the wires have plenty of room to run in between thespaces of the capacitors without increasing the diameter of the pack.The system wires may be run from either of the positive terminal ornegative terminal connectors. The wires (both system and balancing) maybe connected by using butt joints alongside the cell pack or all can berun to another circuit board sitting near the ultracapacitor pack.

In certain embodiments, in order to limit the excess space in theultracapacitors the glass to metal seal can be flipped 180 degrees sothe pin is outside of the can instead of inside. Reduction of thisexcess space in the ultracapacitor serves to limit the amount ofelectrolyte needed inside the capacitor. FIGS. 31A and 31B show howexcess space may be limited by flipping the glass to metal seal so thatthe side with the thicker housing is present on the outside of the cellrather than the inside. Such strategy may be used on any size can withany glass to metal seal that has a body housing that is thicker than thetop cover being used in the can.

2. Housing of the Systems of the Invention

Once the various modular components, including the circuits thatcomprise the MSID, and any HTRES, e.g., ultracapacitors of the presentinvention, have been assembled (i.e., interconnected), these may beinstalled/disposed within a housing. For example, the assembly may beinserted into the housing such as shown in FIG. 39 or FIG. 10. In orderto ensure a mechanically robust system of the invention, as well as forprevention of electrical interference and the like, in some embodiments,encapsulant may be poured into the housing. Generally, the encapsulantfills all void spaces within the housing.

In certain embodiments, the housing size is selected to fit the MSID,e.g., the diameter of the MSID. As such, the dimensions of the outerdiameter may be affected by circuit board diameter of the MSID.

In certain embodiments, the housing contains the MSID, e.g., electronicsmodule only.

In certain embodiments, the housing contains the MSID and the HTRES,e.g., the ultracapacitors of the present invention, e.g., anultracapacitor string of the present invention.

In certain embodiments, the housing comprises a 15 pin connectorcontainment channel. In certain embodiments, the 15 pin connectorcontainment channel comprises a “through all pocket,” or a cut out inthe cap assembly of the housing design to provide a wide turning radiusthat reduces the stress concentration of the wire joint at the exit ofthe Micro-D connector. In this way wire contact with sharp edges and thewall is limited and reduces the risk of wire damage.

In certain embodiments, the housing affords concentric and decoupledmounting of the MSID to 15 pin connector containment channel.

In certain embodiments, the housing comprises an open wire containmentchannel that allows for the MSID and capacitor to be assembledindependent from the housing, which significantly increases themanufacturability of the system. The open wire containment channelprovides for drop in place mounting of the 15 pin Micro-D connector. Ina particular embodiment, the tapered entrance of the open wirecontainment channel limits the contact of the wires with edges andchannel walls.

In certain embodiments, the housing further comprises a removable thinwalled housing cover. In certain embodiments, the removable thin walledhousing chassis cover provides for unobstructed path for wires to berouted along side the MSID structure within the chassis. In a particularembodiment, a radial extrusion of the housing insert provides a mountingface for the removable thin walled cover.

In certain embodiments, the assembly of the MSID and any HTRES mayfurther comprise a 37 pin connector as a removable interface between theelectronics module, e.g., MSID, and HTRES module, e.g., capacitormodule. This removable interface creates the inherent modularity of thesystem.

In certain embodiments, the 37 pin connector may be disposed in aremovable housing interface between separate housings containing theMSID and the HTRES, e.g., an ultracapacitor string described herein.This provides for seamless and repeatable connection disconnection ofelectronics module and capacitor module. In certain embodiments, the 37pin connection, e.g., Micro-D, is axially mounted and reduces the radialfootprint required to secure the connector in place. In certainembodiments, the dual open wire channel of the separate housinginterface accommodates the routing of two sets of wires from the 37 pinMicro-D connector. “Through all pockets” in one or two sides of thehousing interface provides for a wide turning radius for the wires fromthe connector into the open channel.

As such, in one embodiment of the invention, the housing is modular, andcomprises a three component housing system to separately contain (1) theMSID, e.g., in an MSID housing, (2) the HTRES, e.g., the ultracapacitorstrings described herein, e.g., in an HTRES housing, and (3) theconnecting wiring between the two, e.g., in a wiring interface housing.In certain embodiments, each component of the housing system may beseparated into its own housing assembly that separately contains theMSID, the HTRES, or the wiring, e.g., in which each housing component isdesigned to interface with the other housing assemblies. In certainembodiments the connecting wiring between the MSID and the HTRES furthercomprises a connector, e.g., a 37 pin connector. In certain embodiments,the separate wiring interface affords modularity to the housing, whichmay serve to increase serviceability, improve the ease of manufacture,and reduce costs of production and/or maintenance. In certainembodiments, the system is a power system. In certain embodiments, thesystem is a data system.

In certain embodiments, high temperature chemical resistant O-rings,e.g., Viton O-rings, provide secure mounting and dampening which reducesthe transmission of vibration from the pressure to barrel to systemhousing. In a particular embodiment, the O-rings are located at the baseof the 15 and 37 pin connector housings, e.g., and provide forconcentric mounting of the system housing within a pressure barrel.

i. Potting

In certain embodiments, the housing container further comprises anencapsulant that encapsulates the energy storage and the controller,such process also being known as “potting.” In a particular embodiment,the MSID and/or the HTRES may be immersed in an encapsulant forprotection against vibration and shock in high temperature environments

Accordingly, the power and data systems described herein may be“potted,” or inserted into the housing that is then filled withencapsulant. Among other things, the encapsulant provides for damping ofmechanical shock as well as protection from electrical and environmentalinterferences. In one embodiment, the housing is filled with SYLGARD®170 silicone elastomer (available from Dow Corning of Midland, Mich.) asthe encapsulant.

Embodiments of the encapsulant may include, for example, a fast curesilicone elastomer, e.g., SYLGARD 170 (available from Dow Corning ofMidland Mich.), which exhibits a low viscosity prior to curing, adielectric constant at 100 kHz of 2.9, a dielectric strength of 530volts per mil v/mil, and a dissipation factor at 100 Hz of 0.005, and atemperature range of about minus forty five degrees Celsius to about twohundred degrees Celsius. Other encapsulants may be used. An encapsulantmay be selected, for example, according to electrical properties,temperature range, viscosity, hardness, and the like.

ii. Advanced Potting

In certain embodiments, by providing a sufficient number of expansionvoids, e.g., at least one expansion void, in the encapsulation material,e.g. a silicone elastomer gel, in which the controller is potted in thehousing, e.g., using the advanced potting method described herein,deformation of the circuit boards is reduced at high temperatures.

In certain embodiments, advanced potting methods may be utilized toprepare the systems of the present invention, e.g., in the fabricationprocess.

The advanced potting method comprises incorporating the use of removableinserts that are inserted, e.g., radially, through slots in the housingchassis wall. The inserts are placed at high silicone elastomer volumeregions (e.g., centered between boards) during the potting process. Oncesilicone within chassis has cured, inserts are extracted through theslots leaving an air void of equal volume to the insert.

The advanced potting methods provided herein serve to reduce oreliminate circuit board deformation due to the thermal expansion of thesilicone elastomer potting compound. Silicone elastomer has aparticularly high coefficient of thermal expansion and as a resultduring high temperature conditions high stress concentrations develop onthe circuit boards causing plastic deformation.

The advanced potting process creates air voids, e.g., at least one airvoid, at various high volume regions along the controller, e.g., MSIDstructure. During high temperature conditions these air voids provide anexpansion path for the expanding silicone elastomer. As a result, stressconcentrations are drawn away from circuit boards. Reduction in thestress concentrations on the circuit boards also reduces the stress onthe solder joints of the surface mount components.

Moreover, this process may be useful for any potted circuitry subjectedto downhole high temperatures, such as those found in downholeconditions, wherein the high temperature encapsulating potting material

Systems of the Present Invention

In one embodiment, systems of the present invention are comprised of anMSID of the present invention, and a housing structure configured toaccommodate the MSID for placement into a toolstring.

In another embodiment, wherein the system is a power system, the systemcomprises an MSID of the present invention; a high temperaturerechargeable energy storage device (e.g., an ultracapacitor describedherein); and a housing structure in which the MSID and high temperaturerechargeable energy storage device are both disposed for placement intoa toolstring

Generally a power system as described herein affords decoupling of anelectrical aspect of a power source electrical, e.g. voltage, current,or instantaneous power from an electrical aspect of a load.

In one embodiment, systems of the present invention are comprised of anMSID of the present invention, and a housing structure configured toaccommodate the MSID for mounting on or in the collar.

In certain embodiments, the MSID may be configured for data loggingalone.

In certain embodiments, the MSID may be configured as a data system.

In one embodiment, the invention provides a data system (e.g., adaptedfor downhole environments) comprising a controller adapted to receivepower from a power source and configured for data logging; one or moresensor circuits configured to receive (e.g., and interpret) data; andwherein the system is adapted for operation in a temperature range ofbetween about seventy five degrees Celsius to about two hundred and tendegrees Celsius.

In another embodiment, the invention provides a data system (e.g.,adapted for downhole environments) comprising a controller adapted toreceive power from a power source and configured for drillingoptimization; one or more sensor circuits configured to receive (e.g.,and interpret) drilling data in real-time, suitable for modification ofdrilling dynamics; and wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In one embodiment, the invention provides a data system (e.g., adaptedfor downhole environments) comprising a controller adapted to receivepower from a power source and configured to determine torque on bit(TOB); one or more sensor circuits configured to receive (e.g., andinterpret) data; and wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In one embodiment, the invention provides a data system (e.g., adaptedfor downhole environments) comprising a controller adapted to receivepower from a power source and configured to determine weight on bit(WOB); one or more sensor circuits configured to receive (e.g., andinterpret) data; and wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In one embodiment, the invention provides a data system (e.g., adaptedfor downhole environments) comprising a controller adapted to receivepower from a power source and configured to determine temperature by wayof a temperature sensor (e.g., a resistance temperature detector (RTD)which indicates a temperature by way of changing resistance); one ormore sensor circuits configured to receive (e.g., and interpret) data;and wherein the system is adapted for operation in a temperature rangeof between about seventy five degrees Celsius to about two hundred andten degrees Celsius.

In certain embodiments, a plurality of data systems may be employed toanalyze downhole conditions, e.g., vibrations and shocks in multipleareas, as they vary along the length of the drill string or tool string.In a particular embodiment, such spatial measurements may be useful for,among other things, locating, and making distinction of the source ofany problem detected by a sensor. In particular embodiments, to organizedata received from said plurality of data systems described herein, eachmay be assigned an identification or address on a data bus and each maytransmit its information in conjunction with said identification oraddress and/or in response to a request for information from saididentification, or according to a schedule which allocates a certaintime or frequency to MSID with said identification.

A method of improving the efficiency of drilling dynamics, e.g.,compared to currently used systems, comprising using any data system ofthe present invention. In certain embodiments, the method comprisesemploying a plurality of data systems described herein disposed atdifferent locations in the toolstring and/or collar.

In certain embodiments, the controller for data logging is an MSIDconfigured for data logging.

In certain embodiments, the data may be selected from shock, vibration,weight on bit (WOB), torque on bit (TOB), annular pressure andtemperature, and/or hole size.

In certain embodiments, configuring the controller for data loggingcomprises configuring the controller to be capable of monitoring,logging, and communication of system health, e.g., communicatingdownhole information in real-time, e.g., providing real-time monitoringand communication of shocks, vibrations, stick slip, and temperature.

In certain embodiments, the adaptation for operation in a temperaturerange of between about seventy five degrees Celsius to about two hundredand ten degrees Celsius comprises encapsulating the controller with amaterial that reduces deformation of the modular circuits at hightemperatures, e.g. a silicone elastomer gel. In a specific embodiment,the system is adapted for operation in a temperature range of betweenabout seventy five degrees Celsius to about two hundred and ten degreesCelsius by providing sufficient number of expansion voids, e.g., atleast one expansion void, in the encapsulation material in which thecontroller is potted in the housing, e.g., using the advanced pottingmethod described herein.

In certain embodiments, the data logging system further compriseselectrically coupled data storage, e.g., locally or remotely.

In another embodiment, the invention provides a method for data logging,e.g., in a downhole environment, comprising electrically coupling apower source to any data system of the present invention, such that datalogging is enabled.

A method for fabricating a data system of the present inventioncomprising: selecting a controller adapted to receive power from a powersource and configured for data logging, one or more sensor circuitsconfigured to receive (e.g., and interpret) data; and wherein the systemis adapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius; andincorporating controller and said sensor circuits into a housing, suchthat a data system is provided.

In certain embodiments, a reserve power source may be desirable. In thisembodiment, the data system may also comprise a high temperaturerechargeable energy storage (HTRES), e.g., at least one ultracapacitordescribed herein, and a second controller for controlling at least oneof charging and discharging of the energy storage, the second controllercomprising at least one modular circuit configured to intermittentlysupply power to the data controller and sensor circuits when no powerfrom the power source is detected; wherein the system is adapted foroperation in a temperature range of between about seventy five degreesCelsius to about two hundred and ten degrees Celsius

In one embodiment, the data interface system is configured to exhibitone or more of the performance characteristics provided in the followingtable. For clarity, this tabular listing is for convenience alone, andeach characteristic should be considered a separate embodiment of theinvention.

TABLE 3 Exemplary Performance Parameters PARAMETER PerformanceCharacteristic Description VALUE Lateral vibration Measures in twoperpendicular lateral 0 to 40 g RMS  measurement range directionsLateral vibration 1 g RMS measurement resolution Lateral shockmeasurement Measures in two perpendicular lateral 0 to 500 g RMS rangedirections Lateral shock measurement 5 g RMS resolution Axial vibrationmeasurement 0 to 40 g RMS  range Axial vibration measurement 0.5 g RMSresolution Axial shock measurement 0 to 500 g RMS range Axial shockmeasurement 5 g RMS resolution Torsional oscillation Moderate TorsionalVibration 0-0.5 SSI measurement levels Pronounced Torsional Vibration0.5-1 SSI Stick slip measurement Significant Stick Slip 1-2 SSI levelsSevere Stick Slip >2 SSI Vibration Measurements 50 us Time ResolutionShock Time resolution cps: Shock Counts per second 127 cps Memory 0.5MB-2MB RMS value Lateral Vibrations Average value, Maximum value andshock Lateral count shocks Logged Parameters RMS value as fast as each15 s Axial [The various parameters can Vibrations be logged as fast aseach 15 s] Average value and Maximum value as fast as Axial each 15 sShocks Maximum SSI and average SSI Torsional Maximum SSI and average SSIvibrations Average value Stick Slip Temperature Logging Input Voltage 7V to 30 V Input Current <5 mA OD to O-rings 1.5 in OD to Chassis 1.4 in.Length Depends on memory option 5-9 in Operating Temperature The systemcan safely and reliably operate −20° C. to 150° C. for 2000 hours inthis temperature range Survivable Temperature Exposure to 175° C.temperature accelerates −50° C. to 175° C. operating life Maximumcontinuous 15-500 Hz 20 g RMS vibration Maximum shock 0.5 mSec,half-sine 1000 g

In certain embodiments, the MSID may be configured as a power system.

In certain embodiments, the MSID may be configured as a power system andfor data logging.

In configurations of the MSID wherein the MSID is configured as a powersystem, additional modular circuits, comprised of circular circuitboards, may be added to provide additional functionality to the system.Such additional circuits may be added via additional stackers, joiningthe modular bus, wherein the housing is configured/constructed toaccommodate any increase in size of the MSID. Moreover, these additionalcircuits, due to the modular nature of the MSID, do not add additionalcomplication to manufacturing of the MSID other than the addition ofstacked circular circuit board, and may easily be removed for service orremoval of functionality without damage to the remainder of the MSID.

In certain embodiments described herein, the systems of the presentinvention may include a High Temperature Rechargeable Energy Storage(HTRES). The energy storage may include any type of technologypracticable in downhole conditions. In certain embodiments, the HTRES isconfigured for operation at a temperature greater than 75 degreesCelsius, e.g., a temperature that is within a temperature range ofbetween about 75 degrees Celsius to about 210 degrees Celsius, e.g., atemperature that is within a temperature range of between about 85degrees Celsius to about 210 degrees Celsius, e.g., a temperature thatis within a temperature range of between about 95 degrees Celsius toabout 100 degrees Celsius, e.g., a temperature that is within atemperature range of between about 75 degrees Celsius to about 210degrees Celsius, e.g., a temperature that is within a temperature rangeof between about 110 degrees Celsius to about 210 degrees Celsius, e.g.,a temperature that is within a temperature range of between about 120degrees Celsius to about 210 degrees Celsius, e.g., a temperature thatis within a temperature range of between about 130 degrees Celsius toabout 210 degrees Celsius, e.g., a temperature that is within atemperature range of between about 140 degrees Celsius to about 210degrees Celsius, e.g., a temperature that is within a temperature rangeof between about 150 degrees Celsius to about 210 degrees Celsius, e.g.,a temperature that is within a temperature range of between about 160degrees Celsius to about 210 degrees Celsius, e.g., a temperature thatis within a temperature range of between about 170 degrees Celsius toabout 210 degrees Celsius, e.g., a temperature that is within atemperature range of between about 175 degrees Celsius to about 210degrees Celsius.

In certain embodiments of the invention, the energy storage, or HTRESincludes at least one ultracapacitor (which is described below withreference to FIG. 3).

Additional embodiments of HTRES include, without limitation, chemicalbatteries, for instance aluminum electrolytic capacitors, tantalumcapacitors, ceramic and metal film capacitors, hybrid capacitorsmagnetic energy storage, for instance, air core or high temperature corematerial inductors. Other types of that may also be suitable include,for instance, mechanical energy storage devices, such as fly wheels,spring systems, spring-mass systems, mass systems, thermal capacitysystems (for instance those based on high thermal capacity liquids orsolids or phase change materials), hydraulic or pneumatic systems. Oneexample is the high temperature hybrid capacitor available from EvansCapacitor Company Providence, R.I. USA part number HC2D060122DSCC10004-16 rated for 125 degrees Celsius. Another example is the hightemperature tantalum capacitor available from Evans Capacitor CompanyProvidence, R.I. USA part number HC2D050152HT rated to 200 degreesCelsius. Yet another example is an aluminum electrolytic capacitoravailable from EPCOS Munich, Germany part number B41691A8107Q7, which israted to 150 degrees Celsius. Yet another example is the inductoravailable from Panasonic Tokyo, Japan part number ETQ-P5M470YFM ratedfor 150 degrees Celsius. Additional embodiments are available from Saft,Bagnolet, France (part number Li-ion VL 32600-125) operating up to 125degrees Celsius with 30 charge-discharge cycles, as well as a li-ionbattery (experimental) operable up to about 250 degrees Celsius, and inexperimental phase with Sadoway, Hu, of Solid Energy in Cambridge, Mass.

The power systems of the present invention, which comprise an MSIDdescribed herein, are useful for acting as a buffer for power suppliedby a source to a load. This buffering system comprises numerousadvantages over the existing systems which typically use a directconnection of the power source to the load. Such advantages include thecapability to optimize one or more performance parameters of efficiency,power output, battery lifetime, or HTRES (e.g., ultracapacitor)lifetime.

Accordingly, one embodiment of the invention provides a power systemadapted for buffering the power from a power source to a load, e.g., ina downhole environment, comprising: a high temperature rechargeableenergy storage (HTRES), e.g., at least one ultracapacitor describedherein, and a controller for controlling at least one of charging anddischarging of the energy storage, the controller comprising at leastone modular circuit configured for reducing battery consumption bygreater than 30%, e.g., greater than 35%, e.g., greater than 40%, e.g.,greater than 45%, e.g., greater than 50% (e.g., as compared to thebattery consumption with the power system); wherein the system isadapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius.

In another embodiment, the invention provides a power system adapted forbuffering the power from a power source to a load in a downholeenvironment comprising: a high temperature rechargeable energy storage(HTRES), e.g., at least one ultracapacitor described herein, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured for increasing battery run time (i.e., battery life,or operational hours) by greater than 50%, e.g., greater than 60%, e.g.,greater than 70%, e.g., greater than 80%, e.g., greater than 90%, e.g.,greater than 100% (e.g., as compared to the battery consumption with thepower system); wherein the system is adapted for operation in atemperature range of between about seventy five degrees Celsius to abouttwo hundred and ten degrees Celsius.

In another embodiment, the invention provides a power system adapted forbuffering the power from a power source to a load, e.g., in a downholeenvironment, comprising: a high temperature rechargeable energy storage(HTRES), e.g., at least one ultracapacitor described herein, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured for increasing the operating efficiency to greaterthan 90%, e.g., greater than 95%; wherein the system is adapted foroperation in a temperature range of between about seventy five degreesCelsius to about two hundred and ten degrees Celsius.

In another embodiment, the invention provides a power system adapted forbuffering the power from a battery power source to a load, e.g., in adownhole environment, comprising: a high temperature rechargeable energystorage (HTRES), e.g., at least one ultracapacitor described herein, anda controller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured to draw a constant current from the battery andconstant output voltage across the battery discharge; wherein the systemis adapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius.Moreover, the management of the constant current draw from the batterywith a constant output voltage across the battery discharge serves todecrease the battery consumption rate by optimizing for the needs of agiven battery.

In another embodiment, the invention provides a power system adapted forbuffering the power from a power source to a load, e.g., in a downholeenvironment, comprising: a high temperature rechargeable energy storage(HTRES), e.g., at least one ultracapacitor described herein, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured to control the input current (e.g., ranging fromabout 2 A to about 10 A) from the power source and output HTRES voltage;wherein the system is adapted for operation in a temperature range ofbetween about seventy five degrees Celsius to about two hundred and tendegrees Celsius. In certain embodiments, the voltage is selected basedupon the load. In a particular embodiment, the load may vary, and therequired voltage will also vary accordingly. In certain embodiments,including a varying voltage, the power system is configured to adopt theoptimum stable lowest voltage to reduce the current draw on the powersource, e.g., the battery, wherein the voltage remains stable withinplus or minus 2V, e.g., within plus or minus 1V. Importantly, it iswell-known that voltage stability increases the longevity of the load aswell as the battery life. Furthermore, in certain embodiments, thestable lowest voltage ranges from about 0V to about 10V; from about 10Vto about 20V; from about 20V to about 30V; from about 30V to about 40V;from about 40V to about 50V; from about 50V to about 60V; or from about60V to about 100V.

In another embodiment, the invention provides a power system adapted forbuffering the power from a power source to a load, e.g., in a downholeenvironment, comprising: a high temperature rechargeable energy storage(HTRES), e.g., at least one ultracapacitor described herein, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured to control the input power (e.g., ranging from about0 W to about 100 W) from the power source and output HTRES voltage;wherein the system is adapted for operation in a temperature range ofbetween about seventy five degrees Celsius to about two hundred and tendegrees Celsius. In certain embodiments, the voltage is selected basedupon the load. In a particular embodiment, the load may vary, and therequired voltage will also vary accordingly. In certain embodiments,including a varying voltage, the power system is configured to adopt theoptimum stable lowest voltage to reduce the power draw on the powersource, e.g., the battery, wherein the voltage remains stable withinplus or minus 2V, e.g., within plus or minus 1V. Importantly, it iswell-known that voltage stability increases the longevity of the load aswell as the battery life. Furthermore, in certain embodiments, thestable lowest voltage ranges from about 0V to about 10V; from about 10Vto about 20V; from about 20V to about 30V; from about 30V to about 40V;from about 40V to about 50V; from about 50V to about 60V; or from about60V to about 100V.

In another embodiment, the invention provides a method for buffering thepower from a power source to a load, e.g., in a downhole environment,comprising electrically coupling a power source to any power system ofthe present invention, and electrically coupling said power system to aload, such that the power is buffered from the power source to the load.

A method for fabricating a power system of the present inventioncomprising: selecting a high temperature rechargeable energy storage(HTRES), e.g., at least one ultracapacitor described herein, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured to control the buffering of power from a power sourceto a load; and incorporating the HTRES and controller into a housing,such that a power system is provided.

In certain embodiments of the power and/or data systems of the presentinvention, the power system is adapted for operation in a temperaturerange of between about seventy five degrees Celsius to about two hundredand ten degrees Celsius, e.g., between about 80 degrees Celsius to abouttwo hundred and ten degrees Celsius, e.g., between about 90 degreesCelsius to about two hundred and ten degrees Celsius, e.g., betweenabout 100 degrees Celsius to about two hundred and ten degrees Celsius,e.g., between about 110 degrees Celsius to about two hundred and tendegrees Celsius, e.g., between about 120 degrees Celsius to about twohundred and ten degrees Celsius, e.g., between about 125 degrees Celsiusto about two hundred and ten degrees Celsius, e.g., between about 130degrees Celsius to about two hundred and ten degrees Celsius, e.g.,between about 140 degrees Celsius to about two hundred and ten degreesCelsius, e.g., between about 150 degrees Celsius to about two hundredand ten degrees Celsius, e.g., between about 160 degrees Celsius toabout two hundred and ten degrees Celsius, e.g., between about 175degrees Celsius to about two hundred and ten degrees Celsius. In certainembodiments of the power system of the present invention, the powersystem is adapted for operation in a temperature range of between aboutseventy five degrees Celsius to about 150 degrees Celsius, e.g., betweenabout 100 degrees Celsius to about 150 degrees Celsius, e.g., betweenabout 125 degrees Celsius to about 150 degrees Celsius.

In certain embodiments of the power and/or data systems of the presentinvention, the power system further comprises a housing, e.g., anadvanced modular housing described herein, in which the controller(e.g., an MSID of the present invention) and any HTRES (e.g., anultracapacitor string of the invention) are disposed, for example,wherein the housing is suitable for disposition in a tool string. Inparticular embodiments, the controller is encapsulated with a materialthat reduces deformation of the modular circuits at high temperatures,e.g. a silicone elastomer gel. In a specific embodiment, the system isadapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius byproviding sufficient number of expansion voids, e.g., at least oneexpansion void, in the encapsulation material in which the controller ispotted in the housing, e.g., using the advanced potting method describedherein.

In certain embodiments of the power system of the present invention, thecontroller is an MSID of the present invention. In certain embodiments,the MSID comprises a junction circuit board, e.g., wherein said junctioncircuit board is adapted to communicate with externalcomputers/networks. In certain embodiments, the MSID comprises a crossover circuit board. In certain embodiments, the MSID comprises anultracapacitor charger circuit. In certain embodiments, the MSIDcomprises an ultracapacitor management system circuit. In certainembodiments, the MSID comprises an electronic management system circuit.In certain embodiments, the MSID comprises an ultracapacitor chargercircuit. And in certain embodiments, the MSID comprises any combinationof a junction circuit board electrically connected to a power source, anultracapacitor charger circuit, an ultracapacitor management systemcircuit, and an electronic management system circuit.

In certain embodiments of the power and/or data systems of the presentinvention, the HTRES comprises a plurality of HTRES cells.

In certain embodiments of the power and/or data systems of the presentinvention, the HTRES is an ultracapacitor string described herein.

In certain embodiments of the power and/or data systems of the presentinvention, the power source comprises a wireline power source

In certain embodiments of the power and/or data systems of the presentinvention, the power source comprises two batteries.

In certain embodiments of the power and/or data systems of the presentinvention, the power source comprises a wireline power source, and onebattery, e.g., a backup battery.

In certain embodiments of the power systems of the present invention,the load comprises at least one of electronic circuitry, a transformer,an amplifier, a servo, a processor, data storage, a pump, a motor, asensor, a thermally tunable sensor, an optical sensor, a transducer,fiber optics, a light source, a scintillator, a pulser, a hydraulicactuator, an antenna, a single channel analyzer, a multi-channelanalyzer, a radiation detector, an accelerometer and a magnetometer.

In certain embodiments of the power systems of the present invention,the controller circuit may also be configured to provide intermittentpower pulses, e.g., between about 50 W and 100 W.

An additional advantage of the power systems of the present invention iseach highly functional system may be made without lithium.

In certain embodiments of the power system of the invention, the powersystem provides voltage stability to the entire tool string and allassociated electronics. Such voltage stability affords a voltage stablemicro-grid that that improves the lifetime of said electronics sensitiveto voltage swings.

In certain embodiments of the power system of the invention, the powersystem may communicate downhole information in real-time.

In certain embodiments of the power system of the invention, the powersystem may provide real-time monitoring and communication of shocks,vibrations, stick slip, and temperature.

In certain embodiments of the power system of the invention, the powersystem may provide monitoring, logging, and communication of systemhealth.

In certain embodiments of the power system of the invention, the powersystem may provide monitoring and communication of battery state ofcharge monitoring in real time or off line.

In certain embodiments of the power system of the invention, the powersystem may further comprise a surface decoding system.

In certain embodiments of the power system of the invention, the powersystem may directly drive motor pulsers

In certain embodiments of the power system of the invention, the powersystem increases safety by allowing moderate rate cells to be used wherehigh rate cells were necessary.

In certain embodiments of the power system of the invention, the powersystem may provide increased reliability with less Lithium useddownhole.

In certain embodiments, wherein solenoid based or motor based mudpulsers are used in MWD and LWD tool strings, the power systems of thepresent invention may improve the reliability of the mud pulser, and/orimprove signal integrity of the pulses.

In another embodiment, the present invention provides a power sourceelectrically coupled to any power system of the present invention, and aload adapted for operation in a downhole environment.

1. Systems for High Efficiency Applications

(a) Efficiency Optimization

In certain embodiments, the MSID may be configured to afford efficiencyoptimization of the power system. Efficiency of the power electronicscan be generally described as the ratio between output power deliveredto the load and input power being delivered by a power source, such asbatteries, a wireline or a generator. In some embodiments, the EMScircuit is capable of measuring input voltage and input currentdirectly, calculating input power as the product of the twomeasurements. Likewise, the EMS circuit is capable of measuring outputvoltage and current, calculating output power as the product of the twomeasurements.

Through its communication to other circuits, e.g. the UCC circuit, theEMS circuit is capable of commanding parameters such as charge currentand charge time. This can enable control of both input current andoutput voltage. By varying the charge current and regulated outputvoltage, the EMS circuit is able to quantify the electronics powerefficiency across the entire operating range of charge current andcapacitor voltage.

In one embodiment, the MSID optimizes power electronics efficiency,e.g., through the use of the EMS and through the use of hystereticvoltage regulation whereby the charge current is switched between achosen high current level and zero current level. The reason for this isthat often power electronics operate most efficiency at the mid to upperrange of their power capability range. Additionally, when the powerelectronics are not processing a charge current, they can be put into alow power draw state. The low power state draws only the quiescent powerof each circuit. Therefore, by configuring the power system through theEMS circuit for intermittently charging ultracapacitors at a highcurrent level for a short period of time followed by a long, low powerdraw “off” state, very high electronics efficiency can be achieved.

In one embodiment, through continuous measuring and control of chargecurrent, the EMS circuit is capable of modifying the behavior of thepower electronics to, in certain embodiments, achieve maximumefficiency. This real-time adjustment capability is important in orderto adjust to changes in temperature, output load, capacitor efficiency,and battery efficiency.

The overall electronics efficiency is dependent on many differentfactors that vary with such variables as temperature and input voltage.The EMS circuit is able to accurately measure efficiency by calculatingthe ratio of output power to input power. However, it is difficult topredict which operating point is the most efficient in any givenenvironment. Therefore, the EMS circuit employs a technique known as“hill climbing”. The hill climbing method involves creating frequentperturbations to the charge current and observations of system behavior.After each perturbation, or change of the charge current, the totalefficiency is calculated. If the change in charge current resulted inhigher efficiency, the charge current is further changed in the samedirection. If the change in charge current resulted in less efficiency,the charge current is changed in the opposite direction. In this way,the hill climbing method targets an operating point at which the powerelectronics operate at or near peak efficiency.

In certain embodiments, the MSID also optimizes for efficiency bytargeting low power modes of operation for the UCC circuit. For example,in some embodiments, the UCC circuit functions as a buck and a boostpower converter together. In the buck-boost mode of operation, fourtransistors are being switched to regulate the charge current. On theother hand, in either buck or boost modes of operation, only twotransistors are being switched to regulate the charge current.Therefore, buck-boost mode generally operates with lesser efficiencythan either buck or boost modes. Transitions between buck, buck-boost,and boost modes are governed by the charge current and capacitorvoltage. Since both the charge current and capacitor voltage may bemeasured by the other circuits, e.g. the EMS circuit, the MSID cancontrol the UCC charge current and capacitor voltage to ensure that theUCC operates in the buck and boost modes for as long as possible for thebest efficiency.

In certain embodiments, various circuits or sub circuits may enter a lowpower sleep state to conserve power. In some embodiments, said sleepstates are activated locally by circuits or by a circuit's digitalsupervisor. In some embodiments, said sleep states are activatedcentrally, e.g. by an EMS circuit, e.g. by way of a modular bus, e.g. byway or an EMS circuit communicating over a modular bus to a digitalsupervisor. For example, a UMS circuit may not need to operatecontinuously, but only intermittently and, in some embodiments, onlywhen balancing of capacitors is needed. A UMS circuit may measure orreport a substantially balanced state of a capacitor string and thenenter a sleep state in methods as described above. Similar schemes maygenerally be applied to other circuits as well. For instance, if acapacitor string does not need to be charged, an ultracapacitor chargermay enter a sleep state.

(b) Power Optimization

In certain embodiments, the MSID may be configured to afford poweroptimization of the power system. For example, in some embodiments, theEMS circuit is capable of adjusting output power capabilities inreal-time to accommodate for changing load requirements. Theultracapacitors are able to safely store a range of voltage levels,e.g., further dependent on the number and size of the ultracapacitors.At high voltage levels, the output power capability of theultracapacitors is increased. That is, the ultracapacitors can sustainhigh power output levels for a long period of time before beingrecharged. At lower voltage levels, the ultracapacitors cannot sustainas high of power levels but overall efficiency may be increased in orderto extend battery lifetime.

(c) Voltage Optimization

In certain embodiments, the MSID may be configured to optimize a voltagepresented to a load. For example, an MSID or a user, may measure lowerpower draw at voltages within a certain range and choose to operate insaid range to extend, for instance battery lifetime. For example, anMSID may control a power system to operate with a load voltage in arange from 50 to 100 V, from 40 to 50 V, from 30 to 40 V, from 25 to 30V, from 20 to 25 V, from 15 to 20 V, from 10 to 15 V, from 0 to 10V.

(d) Battery Lifetime Optimization

In certain embodiments, the MSID may be configured to afford batterylifetime optimization. For example, under certain conditions a batteryoffers longer lifetime given a steady current draw as opposed tointermittent high current draw. Under other conditions, a battery offerslonger lifetime given a pulsed current draw, a current draw having highfrequency content, a mildly varying current draw, a combination of theabove or the like. As such, in certain embodiments, these heuristics canbe utilized to shape the battery current draw in order to optimize forbattery lifetime. Further, these heuristics may be applied in run-timebased on sensed parameters, i.e. having a determination of theconditions that determine the optimum battery current draw. In oneexample, battery current is smoothed at high temperatures to decreasecathode freeze-over in Lithium Thionyl Chloride cells, but includespulses at low temperatures to encourage de-passivation of the samecells. In a particular embodiment, a hysteretic control scheme can beutilized with a non-zero low hysteresis level. By varying the chargecurrent between two non-zero current states, capacitor voltageregulation may be achieved while reducing the negative effect of large,fast deviations in battery current draw on the health of the batteries,e.g., lithium thionyl chloride batteries. Generally, a smoother currentyields a more efficient extraction of energy from a source having aseries resistance aspect due to the squared relationship between currentand conduction loss.As an example, a lithium thionyl chloride battery pack was first drawnwith an ON-OFF current scheme using a power system as disclosed herein.Said battery pack in said first test achieved a lifetime of about 256hours. In a second test, an equivalent battery pack was drawn with asmoothed current scheme using a power system as disclosed herein. Saidbattery pack in said second test achieved a lifetime of about 365 hours.In certain embodiments, the MSID by controlling an aspect of batterycurrent, a battery lifetime may be extended. In certain embodiments apower system comprises said MSID and HTRES.In certain embodiments, a battery current is controlled to fall within arange of less than +/−51% of an average, e.g. less than 50%, e.g. lessthan 40%, e.g. less than 30%, e.g. less than 20%, e.g. less than 20%,e.g. less than 10%.In certain embodiments, a battery current is controlled to includepulses of less than about 1,000 ms and up to about 5 A peak, e.g. lessthan about 500 ms and up to about 2 A peak, e.g. less than about 100 msand up to about 1 A peak. In certain embodiments, a battery current iscontrolled to change no faster than 1 A/sec, e.g. no faster than 0.5A/sec, e.g. no faster than 0.25 A/sec, e.g. no faster than 0.1 A/sec,e.g. no faster than 0.01 A/sec.In certain embodiments, a battery current is controlled to achieve oneof smoothing, pulsing, or shaping. In further embodiments, said batterycurrent is controlled according to measured ambient conditions.

In certain embodiments, the MSID by configuring the power system via theEMS circuit by narrowing the hysteresis range of the charge current,battery current may be made smoother, extending battery lifetime.Generally, a smoother current yields a more efficient extraction ofenergy from a source, mathematically, due to the squared relationshipbetween current and conduction losses.

In another embodiment, the power system, via the EMS circuit, isconfigured to operate using a linear feedback control scheme.

In both hysteretic and linear control embodiments, heuristics concerningbattery chemistry, capacitor chemistry, and power electronics behaviorcan be implemented to further improve system performance.

In certain embodiments, a damaged battery will exhibit high effectiveseries resistance (ESR) that reduces its power capabilities. As such, bycommunicating with the cross over circuit, battery state of chargecircuit information can be logged. Furthermore, by measuring inputbattery current and input battery voltage, battery ESR can be measuredby the EMS circuit. Given excessive ESR, the EMS circuit can command thecross over circuit to switch the battery supply to improve powerhandling capabilities.

(e) HTRES Lifetime Optimization

In certain embodiments, the MSID may be configured to afford HTRES,e.g., ultracapacitor, lifetime optimization to the power system. Forexample, the EMS circuit may be capable of communicating data andcommands to the UMS circuit. This is beneficial for regulating each cellto the desired voltage level even as the regulated output voltagechanges during optimization. Additionally, the UMS circuit reports cellhealth to the EMS circuit via the modular bus. If the UMS circuitreports that one or multiple capacitors are damaged, the EMS circuit canalter the control scheme to mitigate further damage and prolong systemhealth. A damaged cell may exhibit decreased capacitance, such that thecell will charge and discharge faster than surrounding cells. A damagedcell may also exhibit high leakage currents, such that the cell will beconstantly discharging, forcing other cells to obtain a higher voltage.In both cases, it is beneficial to charge the capacitor string to alower voltage. As such, by configuring the power system, e.g., byconfiguring the EMS circuit to communicate with the UMS circuit, it ispossible to isolate cell damage and regulate to a lower capacitorvoltage to preserve capacitor health.

It should also be noted that frequent balancing of ultracapacitorsreduces system efficiency. Passive balancing of cells reduces cellvoltages by passing excess charge through a resistive element.Furthermore, both active and passive balancing requires frequentswitching of MOSFETS, consuming additional power. Therefore, by reducingthe need for cell balancing the EMS circuit can help to reduce powerconsumption and improve system efficiency.

In one embodiment, the power system is configured to exhibit one or moreof the performance characteristics provided in the following table. Forclarity, this tabular listing is for convenience alone, and eachcharacteristic should be considered a separate embodiment of theinvention.

TABLE 4 Exemplary Performance Parameters PARAMETER PerformanceCharacteristic Description VALUE Rated Output Peak Peak power 50 W PowerMaximum Peak Power Maximum Pulse power that can be extracted 100 W fromthe power system Rated Output Voltage Set output voltage can beconfigured based Customizable on power system needs Maximum OutputMaximum output voltage the power system 28 V Voltage can be set toprovide Rated Output Current Pulse output current supported incontinuous 2.5 A operation Maximum output current Peak Pulse outputcurrent during peak power 5 A Input Voltage Acceptable input voltage canvary widely 8 V to 28 V Charging Current The maximum charging currentcan be set to Customizable allow for maximum battery usage Efficiencyduring During a directional job the efficiency of the >90% standardoperation system will to be greater than 90% Diameter 1.4 in is thediameter of the metal chasse and 1.4 in-1.5 in 1.5 in is the diameter ofthe o-ring Length The system length might varies depending on 19 in theoptions selected Functional Temperature The system can safely andreliably operate −20° C. to 150° C. for at least 4000 hours in thistemperature range Survivable Temperature While the system can withstandthis −50° C. to 175° C. temperature range, exposure at 175° C.temperature reduces rapidly its operating life Maximum random 15-500 Hz20 g RMS vibrations Maximum shocks 0.5 mSec, half-sine 1000 g

2. Systems for High Power Applications

The power systems described above, characterized by the advantagesdescribed above, may be configured to provide for relatively high power,e.g. more power than was practically available downhole in prior art.Generally, high power may be provided in a pulsed or intermittentfashion, e.g. not indefinitely, because a power balance must bemaintained between a source and a load and a source may not generally becapable of providing said relatively high power. More specifically, andby way of example, a power system of the present invention may charge aHTRES for a first length of time and provide high power by directingenergy from said HTRES to a load for a second length of time. Aspectsthat characterize a power system of the present invention specificallyfor relatively high power include high voltage and low resistance.Generally, because high power will translate to a high rate of energytransfer, a power system of the present invention may also benefit froma relatively high energy capacity HTRES. For example, a primary battery,e.g. a lithium Thionyl chloride battery for downhole applicationscomprising 8 DD size cells of moderate rate configuration may providefor a maximum of about 10-50 W of power. In comparison a power system ofthe present invention may provide for about up to 5,000 W of power.

By providing for high power, a power system of the present inventionequivalently provides for a voltage stabilization effect of a sharedvoltage in a larger system. Specifically, a high power capability isenabled by a low resistance output and a low resistance output enables arelatively high power output with a relatively low resulting voltagedrop. For instance an HTRES of the present invention may comprise hightemperature ultracapacitors as disclosed herein with a string voltage ofabout 28 V and a resistance of about 100 mOhms. Said exemplary powersystem may provide for about 20 A of output current with a voltagedeviation of only 2 V. The resulting power is approximately 520 W inthis example. Said voltage stabilization effect may be further benefitedby the use of a regulated power converter, e.g. an exemplary loadconverter as disclosed herein. In certain embodiments, the HTREScomprises one or more ultracapacitors described herein, e.g.,ultracapacitor strings. Such ultracapacitor strings, in certainembodiments, are designed to fit within a housing structured with aninner diameter that is dictated by the outer diameter of the circularcircuit boards, and wherein the outer diameter of the housing isdesigned to be accommodated by the tool string. Accordingly, inembodiments wherein the HTRES is comprised of the ultracapacitors of thepresent invention, and are organized in a space efficient ultracapacitorstring orientation, as described herein, larger capacitances areproduced by longer ultracapacitor strings. In certain embodiments, theultracapacitor strings are comprised of 12 capacitors

In certain embodiments, a power system of the present invention mayprovide for about up to 5,000 W of power, e.g. for about 1,000-5,000 Wof power, e.g. for about 500-1,000 W of power, e.g. for about 250-500 Wof power, e.g. for about 100-250 W of power, e.g. for about 51 to 100 Wof power.

Accordingly, another power system embodiment of the invention provides apower system adapted for buffering the power from a power sourcesupplying about 1 W to about 99 W in a downhole environment comprising:a high temperature rechargeable energy storage (HTRES), e.g., anultracapacitor string organized in a space efficient orientation asdescribed herein, and a controller for controlling at least one ofcharging and discharging of the energy storage, the controllercomprising at least one modular circuit configured for providingintermittent high-power pulses, e.g., between about 100 W and 500 W;wherein the system is adapted for operation in a temperature range ofbetween about seventy five degrees Celsius to about two hundred and tendegrees Celsius. In certain embodiments, the HTRES is characterized by acapacitance of about 1-10,000 F. In certain embodiments, the controlleris configured to drive the output at a greater voltage than the inputvoltage. With the added power supplied by high-power pulses, it ispossible to drive a load harder while maintaining battery life. Forexample, this configuration may be used to drive the mud pulser harder(e.g., a solenoid based or motor based mud pulser), which translates tosharper pressure pulses and potentially faster data rates fortransmission to the surface, e.g., up to twice the data rates whilemaintaining battery life and without compromising signal integrity,e.g., using mud pulse telemetry. In another embodiment, the load on thispower system may be an EM transmitter. In another embodiment, the loadon this power system may be a motor drive, e.g., a sensorless brushlessDC motor drive.

In certain embodiments, the power source may be a battery or a turbinepowered MWD/LWD toolstring.

In certain embodiments, the input power is about 1 W to about 20 W, andthe output is greater than 100 W, e.g., about 100 W to about 500 W.

In certain embodiments, the input power is about 20 W to about 50 W, andthe output is greater than 100 W, e.g., about 100 W to about 500 W.

In certain embodiments, the input power is about 50 W to about 99 W, andthe output is greater than 100 W, e.g., about 100 W to about 500 W.

In certain embodiments, a power system of the present invention providesfor a voltage stabilization effect of a shared voltage in a largersystem, by providing for up to about 500 W, e.g. up to about 250 W, e.g.up to about 100 W, while maintaining a voltage deviation of the sharedvoltage less than about 50%, e.g. less than about 40%, e.g. less thanabout 30%, e.g. less than about 20%, e.g. less than about 10%.

In certain embodiments, a system of the present invention provides forEM telemetry in a well at a depth of up to about 40,000 feet, e.g. up toabout 30,000 feet, e.g. up to about 20,000 feet, e.g. up to about 10,000feet.

In certain embodiments, a system of the present invention provides forEM telemetry in a well at a transmission frequency of up to about 100Hz, e.g. up to about 75 Hz, e.g. up to about 50 Hz, e.g. up to about 25Hz, e.g. up to about 15 Hz.

In certain embodiments, a system of the present invention provides formud pulse telemetry in a well at a depth of up to about 40,000 feet,e.g. up to about 30,000 feet, e.g. up to about 20,000 feet, e.g. up toabout 10,000 feet.

In certain embodiments, a system of the present invention provides formud pulse telemetry in a well at a transmission frequency of up to about40 Hz, e.g. up to about 30 Hz, e.g. up to about 20 Hz, e.g. up to about15 Hz, e.g. up to about 10 Hz.

In one embodiment, the power system is configured to exhibit one or moreof the performance characteristics provided in the following table. Forclarity, this tabular listing is for convenience alone, and eachcharacteristic should be considered a separate embodiment of theinvention.

TABLE 5 Exemplary Performance Parameters PARAMETER PerformanceCharacteristic Description VALUE Rated Output Peak Peak power 200 WPower Maximum Peak Power Maximum Pulse power that can be extracted 500 Wfrom the power system Rated Output Voltage Set output voltage can beconfigured based on Customizable power system needs Maximum OutputMaximum output voltage the power system can 28 V Voltage be set toprovide Rated Output Current Pulse output current supported incontinuous 7 A operation Maximum output current Peak Pulse outputcurrent during peak power 15 A Input Voltage Acceptable input voltagecan vary widely 8 V to 28 V Charging Current The maximum chargingcurrent can be set to Customizable allow for maximum battery usageEfficiency during During a directional job the efficiency of the >90%standard operation system will to be greater than 90% Diameter 1.4 in isthe diameter of the metal chasse and 1.5 1.4 in-1.5 in in is thediameter of the o-ring Length The system length might varies dependingon the 19 in-24 in options selected Functional Temperature The systemcan safely and reliably operate for at −20° C. to 150° C. least 4000hours in this temperature range Survivable Temperature While the systemcan withstand this temperature −50° C. to 175° C. range, exposure at175° C. temperature reduces rapidly its operating life Maximum random15-500 Hz 20 g RMS vibrations Maximum shocks 0.5 mSec, half-sine 1000 g

3. Systems for Intermittent Power Source Applications

In applications in downhole environments that require power foroperation, where such power is intermittently interrupted (e.g., whereinpower is supplied by a turbine powered MWD/LWD toolstring that generatespower derived from the flow of mud through the turbine, and such mudflow is stopped to make adjustments to the toolstring), the powersystems of the present invention configured to supply power to a loadmay be configured to operate as an intermittent power source buffer bydirecting energy stored in a HTRES to the load. Generally, becauserelatively long periods without power, e.g. 5 to 10 minutes, willtranslate to a high cumulative energy requirement of the energy buffer,a power system of the present invention may be aided by a relativelyhigh energy HTRES, for instance one having about 1 to 5 Wh of energystorage. Such systems may be aided with the use of a load drivercircuit.

As such, another power system embodiment of the invention provides apower system adapted for buffering the power from an intermittent powersource e.g., a power source that ceases to provide power for periods oftime, by directing energy stored in the HTRES to the load comprising: ahigh temperature rechargeable energy storage (HTRES), e.g., anultracapacitor string organized in a space efficient orientation asdescribed herein, an optional load driver circuit, and a controller forcontrolling at least one of charging and discharging of the energystorage, wherein the system is adapted for operation in a temperaturerange of between about seventy five degrees Celsius to about two hundredand ten degrees Celsius.

In one embodiment, the system of the present invention comprises amodular signal interface device (MSID) configured as a component of apower system. In one example, the MSID may comprise various circuits.Non-limiting examples include a junction circuit, at least one sensorcircuit, an ultracapacitor charger circuit, an ultracapacitor managementsystem circuit, a changeover circuit, a state of charge circuit, and anelectronic management system circuit.

In one embodiment, the MSID comprises a junction circuit anultracapacitor charger circuit, and ultracapacitor management systemcircuit, and an electronic management system circuit.

In some embodiments, the MSID comprises modular circuit boards. Infurther embodiments the modular circuit boards are circular. In furtherembodiments, the modular circuit boards are stacked. In furtherembodiments, the modular circuit boards are circular and stacked.

In certain embodiments, the power source comprises at least one of awireline power source, a battery, or a generator.

In certain embodiments, the power source comprises at least one battery.In this embodiment, the MSID may further comprise a cross over circuit,particularly when the power source comprises more than battery. Inparticular embodiments, the MSID further comprises a state of chargecircuit board.

In certain embodiments, the power source comprises a wireline, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the power source comprises a generator.

In certain embodiments, the power source comprises a generator, and atleast one battery, e.g., a backup battery. In this embodiment, the MSIDmay further comprise a cross over circuit. In particular embodiments,the MSID further comprises a state of charge circuit.

In certain embodiments, the circuit boards may be combined to providemulti-functional circuit boards.

Accordingly, in another embodiment, the invention is directed to anintermittent power source buffer comprised of a power source supplyingabout 1 W to about 500 W, e.g., a downhole turbine, a high temperaturerechargeable energy storage (HTRES), e.g., an ultracapacitor string(e.g., of 1-100 ultracapacitor cells) organized in a space efficientorientation as described herein, an optional load driver circuit, and acontroller for controlling at least one of charging and discharging ofthe energy storage, the controller comprising at least one modularcircuit configured for providing power; wherein the system is adaptedfor operation in a temperature range of between about seventy fivedegrees Celsius to about two hundred and ten degrees Celsius. In certainembodiments, this power system may be considered to have generatedelectrical output that may be applied to the load. In certainembodiments, the controller is an MSID of the present invention.

In certain embodiments, power may be supplied intermittently for greaterthan 500 hours, e.g., about 500 hours to about 1000 hours, e.g., about1000 hours to about 1500 hours, e.g., for the life of the load.

In certain embodiments, the intermittent power source buffer may providea range of voltage outputs, e.g., selected based upon the requirementsof the load.

4. Systems for EM Telemetry

The primary challenge of telemetry is maintaining high signal to noiseratio when transmitting over noisy or very lossy formations. Lossyformations, such as highly resistive formations, attenuate the signal asit propagates resulting in decreased signal amplitude and consequentlysmaller signal to noise ratio. Excess external noise is summed withtelemetry signal to increase the noise in a received signal. Tocompensate for decreased signal to noise ratio at the receiver, a slowerdata bit-rate is often used, sometimes with additional parity orredundancy bits. The receiver may be band-limited to reduce an overallnoise content, the band-limit being lower bound by the data rate, so alower data rate allows for lower overall noise content at an aspect ofthe receiver. Other methods to compensate for decreased signal to noiseratio at the receiver include increasing a magnitude of an aspect of thetransmitted signal.

The output telemetry amplifier in conjunction with a power systemconfigured to supply high-power may be utilized as a general purposeamplifier in many different scenarios. In one particular embodiment,this configuration may be used for transmitting telemetry signals over aresistive load. In another application, the same power amplifierconfiguration could be utilized for an inductive load, such as a motoror linear actuator.

As such, another power system embodiment of the invention provides apower system adapted for providing for high power or high voltagetelemetry, by directing energy stored in the HTRES to the loadcomprising: a high temperature rechargeable energy storage (HTRES),e.g., an ultracapacitor string organized in a space efficientorientation as described herein, an optional load driver circuit, anamplifier circuit, and a controller for controlling at least one ofcharging and discharging of the energy storage, wherein the system isadapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius. Insome embodiments the amplifier circuit is a Class-D circuit known in theart.

Accordingly, in another embodiment, the invention is directed to atelemetry device comprised of a power source, a high temperaturerechargeable energy storage (HTRES), e.g., an ultracapacitor string(e.g., of 1-100 ultracapacitor cells) organized in a space efficientorientation as described herein, an optional load driver circuit, anamplifier circuit, and a controller for controlling at least one ofcharging and discharging of the energy storage; wherein the system isadapted for operation in a temperature range of between about seventyfive degrees Celsius to about two hundred and ten degrees Celsius. Incertain embodiments, the controller is an MSID of the present invention.In certain embodiments, the amplifier is a class-D amplifier.

In certain embodiments, a class-D amplifier is coupled to a dipoleantenna or at least one electrode configured to wirelessly transmitinformation to the surface. In particular embodiments, the EM telemetrysignal, e.g. at 12 Hz, may be characterized by greater power, voltageand/or current as compared with signals generated with known linearamplifiers currently used for this purpose.

In certain embodiments the power system comprising the amplifier isdisposed physically in a tool string between an antenna and aconventional EM module.

In certain embodiments, the power system is also configured to receive atelemetry signal. In some examples, the controller, and in furtherexamples, specifically, the EMS circuit, is configured to interpret saidreceived telemetry signal.

In certain embodiments, an overall tool string architecture may besimplified by way of an interrupted connection between the antenna andthe conventional aspects of the tool string, e.g. the conventional EMmodulator, the other modules within an MWD or LWD tool string. Theinterrupted connection may comprise the power system comprising theamplifier. For instance, in this configuration, the signal presented bythe conventional EM module may serve as an input signal to the powersystem comprising the amplifier and the power system may provide for anamplified version of said input signal to the load, e.g. the antenna.Additionally, if the power system is configured to receive a signal froma remote location, e.g. the surface, by way of the antenna, the powersystem may receive the signal directly from the antenna in thisconfiguration. Further, if the signal received from the remote locationis intended as a control directive an aspect of the power systemcomprising the amplifier, the power system can respond to said controldirective in a fashion such that other aspects of the tool string areunaffected.

In certain embodiments, the amplifier circuit may be combined with thepower converting load driver circuit to afford one combination circuit.

By amplifying an aspect of the telemetry signal, e.g., power, voltage,or current, a number of benefits may be realized. For example, forconditions that are otherwise fixed, an amplified aspect of thetelemetry signal may lead to a higher signal to noise ratio of thereceived signal. Given that higher signal to noise ratio, tradeoffs maybe made until the signal falls to the minimum detectable signal.Moreover, an attenuation of the telemetry signal may increase with rangeor depth in the formation, with frequency, and with other complicatedparameters that depend on formation makeup. For instance, the system mayenable longer range transmission, e.g. from deeper wells, more robusttransmission, e.g., as is needed through problematic formations, and/or,faster transmission rates, e.g., by increasing the transmissionfrequency. Higher data transmission rates ultimately provide a means forfaster and safer drilling, including faster communication of drillingdynamics to afford drilling optimization.

In certain embodiments, high power is achieved primarily through the useof a low impedance high voltage HTRES and efficient operation of thepower electronics.

In certain embodiments, a power system comprising an amplifier mayachieve high performance by way of two fundamental factors (1) theinclusion of relatively high power (low resistance) HTRES providing forhigh power buffering of the power source, and/or (2) the replacement oflinear amplifiers with switched-mode amplifiers, the former typicallyexhibiting between about 20% and 40% overall efficiency, the lattertypically exhibiting between about 80% and 98% overall efficiency.

Considering highly resistive formations, one way to achieve high powertransmission is by driving the formation with a signal having a largevoltage amplitude. Considering low resistance formations, high powertransmission may be achieved by delivering large current. Thus, incertain embodiments, the output of the amplifier is both high voltageand low impedance. In certain embodiments the amplifier provides for anadjustable aspect. The adjustable aspect can be selected from voltage,current, power, frequency, phase and the like. In certain embodimentswhere the amplifier provides for an adjustable aspect, said aspect maybe adjusted in run-time to optimize a condition, for instance, signalintegrity at the receiver, or power consumption by the power system. Incertain embodiments, a system of the present invention provides for EMtelemetry in a well at a depth of up to about 40,000 feet, e.g. up toabout 30,000 feet, e.g. up to about 20,000 feet, e.g. up to about 10,000feet.

In certain embodiments, a system of the present invention provides forEM telemetry in a well at a transmission frequency of up to about 100Hz, e.g. up to about 75 Hz, e.g. up to about 50 Hz, e.g. up to about 25Hz, e.g. up to about 15 Hz.

In certain embodiments, a system of the present invention may includesome or all of the EM telemetry devices and techniques described in U.S.Provisional Patent Application Serial No. 62/066,337 filed Oct. 20,2014, the entire contents of which are incorporated herein by reference.For example, some embodiments may include a downhole EM telemetry systemthat transmits an EM signal with an output power in the range of 20 W to2 kW, and any sub-range thereof, e.g., with a maximum output power of atleast 200 W, 500, W, 750 W, 1,000 W, 1, 250 W, 1,500 W, 1,750 W, 2, 00 Wor more.

5. Data Systems

In one embodiment, the modular signal interface device (MSID) of thepresent invention may be useful as component of a data system, e.g.,configured for data logging and/or reporting, e.g., in MWD or LWD orother applications. In this embodiment, the data system may comprise anMSID that may comprise modular circuit boards selected from one or moresensor circuit boards, a junction circuit board, an EMS circuit, atleast one memory or memory circuit, and any combination there of, forexample, wherein said junction circuit board may be adapted tocommunicate with external computers/networks. In certain embodiments, adata system may further comprise circuits selected from anultracapacitor charger, an HTRES, and a power interface for receivingpower.

The MSID monitors downhole conditions and can be configured to log inmemory and/or communicate in real-time data and parameters, forinstance, warning levels, levels of downhole shocks, vibrations, stickslip, temperature or other such measurements. Certain advantagesinclude, but are not limited to, the ability to prevent or mitigate therisk of toolstring damage and failure downhole, the ability to log datafor accountability purposes, the ability to log data for repair andmaintenance or service purposes, the ability to affect drillingdynamics, e.g., in real-time, such that drilling may be performed withincreased efficiency, reduced shock, increased rate of penetration(ROP), increased bit performance, reduction of non-productive time (NPT)costs; reduction of fluid kicks and fractures. For example, if a drillbit is stuck, and the bit continues to drill and rotate, the result maybe, for example, increased shock, reduced bit performance due to damage,and increased NPT costs, as well as potential damage to the entireelectronic tool string.

Accordingly, the MSID may monitor one or more conditions such as shock,vibration, weight on bit (WOB), torque on bit (TOB), pressure andtemperature, and hole size, which, for example, may be the related toeffects of underbalanced drilling or air drilling, i.e. in some casescertain conditions are amplified in underbalanced or air drilling, e.g.shock and vibration is generally less dampened in those cases.Monitoring such downhole conditions, in certain embodiments, allows thedriller to increase the effectiveness of drilling parameters and, forexample, reduce the risk of toolstring fatigue, premature trips forfailure, stuck pipe, kicks, downhole battery venting, lost circulation,etc. In certain embodiments, the MSID, e.g., disposed inside a housingdescribed herein, is positioned in the toolstring or the collar of thebit. In certain embodiments, the MSID configured for data logging mayprovide one or more of the following: increased reliability of downholetools, improved directional service, and/or improved tracking of wear ontool for improved replacement economics.

In certain embodiments, the MSID is configured to provide measurementsbased on the use of a unique configuration of sensor circuit boards thatmake available six degrees of freedom, which are composed of threelateral degrees of freedom, x, y, and z, and the rotation around each ofthese axis, x_(r), y_(r), and z_(r).

In certain embodiments, the MSID is configured to provide downhole rpmmeasurements, e.g., rotational velocity of the toolstring or bit, weighton bit measurements, and torque on bit measurements.

In certain embodiments, the MSID is configured to provide downhole rpmmeasurements, e.g., rotational velocity of the toolstring or bit.

In certain embodiments, the MSID is configured to provide weight on bitmeasurements, and torque on bit measurements.

In certain embodiments, the MSID is configured to provide torque on bitmeasurements.

In certain embodiments, the power source comprises a wireline powersource.

In certain embodiments, the power source comprises a generator.

In certain embodiments, the power source comprises a battery.

In certain embodiments, the power source comprises two batteries. Inthis embodiment, the MSID may further comprise a cross over circuitboard. In particular embodiments, the MSID further comprises a state ofcharge circuit board.

In certain embodiments, the power source comprises a wireline powersource, and at least one battery, e.g., a backup battery. In thisembodiment, the MSID may further comprise a cross over circuit board. Inparticular embodiments, the MSID further comprises a state of chargecircuit board electrically connected to junction circuit board.

In certain embodiments, the MSID configured for data logging is disposedin a housing alone, e.g., without an HTRES, e.g., one or moreultracapacitors described herein.

In certain embodiments, the MSID configured for data logging is disposedin housing along with an HTRES, e.g., one or more ultracapacitorsdescribed herein. For example, the MSID may be disposed in a housingalong with an ultracapacitor string described herein, e.g., for use as abackup power source.

In certain embodiments, the MSID is connected to external components bya modular connection, e.g., a universal connector pin configuration.

As described above for the general composition of the MSID, the MSID maybe constructed using, stacked circuit boards, e.g., stacked circularcircuit boards, and a modular bus. In certain embodiments, the MSID maybenefit from potting or encapsulating, e.g., using the advanced pottingtechniques described herein.

In certain embodiments, the modular boards are circular, e.g., with adiameter of less than 1.5 inches, e.g. less than 1.49 inches, e.g. lessthan 1.48 inches, e.g. less than 1.475 inches, e.g. less than 1.4inches, e.g. less than 1.375 inches, e.g. less than 1.3 inches, e.g.less than 1.275 inches, e.g. less than 1.251 inches.

In certain embodiments, an MSID (e.g., disposed in a housing) may berelatively small compared to known standards, e.g., less than 12 incheslong, e.g., less than 11 inches long, e.g., less than 10 inches long,e.g., less than 9 inches long, e.g., less than 8 inches long, e.g., lessthan 7 inches long, e.g., less than 6 inches long, e.g., less than 5inches long, e.g., less than 4 inches long. Said MSID may then bereadily disposed at various locations along a drill string or toolstring. In this way, a plurality of MSID's may be employed to indicate,for instance, downhole conditions as they vary along the length of thedrill string or tool string. Such spatial measurements may be usefulfor, among other things, locating, and making distinction of the sourceof a troublesome excitation, for example, whether it be an aspect of thedrill string or tool string itself or an aspect of the formation orother well components, or an aspect of an interaction among saidaspects, characterizing the spatial response of the toolstring tovarious excitations, further identifying potentially hazardous downholeeffects such as stick slip or whirl, or identifying weak aspects of asystem. To organize data received from said plurality of MSID, each maybe assigned an identification or address on a data bus and each maytransmit its information in conjunction with said identification oraddress and/or in response to a request for information relating to saididentification or address, or according to a schedule which allocates acertain time or frequency to MSID with said identification or address.

In certain embodiments, an MSID may provide for logging and/or reportingof downhole conditions. Logging generally entails storing of data orinformation in memory. In particular embodiments, the MSID may beconfigured to provide that the memory may be interrogated at a latertime, for instance, once the MSID is on surface. Alternatively,reporting may entail transmitting data from a downhole environment to aremote location for instance to the surface. Said reporting may beaccomplished effectively in near real-time, or with a delay. Reportingfeatures may exist in systems also having logging features. Reportingfeatures may compliment logging features, e.g., reporting mayinterrogate a local memory while a system is still downhole to reportinformation that had been previously logged.

In certain embodiments, the MSID configured for data logging may becoupled with a tool string data bus. In this way, the MSID may providefor information to be transmitted to the surface, for example, using thetransmission taking place by way of telemetry systems already orotherwise incorporated into the tool string. For example, a tool stringmicroprocessor unit (MPU) module may interpret data bus signalsoriginating from the MSID and input those to a mud pulse telemetrysystem. The mud pulse telemetry system and specifically the mud pulsermay then transmit the data to a surface system by way of mud pulsetelemetry known in the industry. In an alternative embodiment, theinformation from the MSID may utilize electromagnetic (EM) telemetry,also known in the industry.

In certain embodiments, the MSID may comprise a circuit useful fordetecting a fault in any part of the tool string, e.g., in real-time. Ina particular embodiment, the MSID configured for data logging may becoupled with a tool string data bus to afford this detection of a fault.

In certain embodiments, an MSID may provide for an “interrupt-style”telemetry scheme to the surface. In these examples, information may betransmitted to the surface for instance by methods leveraging toolstring telemetry, e.g., well-known in the art or as described herein.The interrupt style communication scheme may override usual datatransmissions to the surface, e.g., data transmissions needed tocontinue drilling operations. In this way, warnings of downholeconditions that should be addressed (hazardous conditions), for instanceby stopping drilling operations, may force operators to stop drillingoperations, e.g., by starving them of needed information or power.Drilling operators may remedy the situation leading to hazardousconditions and then continue drilling. In this way, an overallreliability of downhole systems may be improved. Additionally, incertain embodiments, a record of deviations from recommended practicesmay be logged.

In certain embodiments with interrupt-style communication, datatransmitted to the surface may comprise warning information or raw datathat would indicate certain conditions, or data otherwise parameterizedor configured in a manner deemed useful by the designer or user. Forexample, levels of continuous vibration may be mapped to warning levelsor warning signals indicating a level of severity. Similarly, levels ofshock, temperature, anomalies in torque on bit (TOB) or weight on bit(WOB) or other downhole effects that may be hazardous may be mapped towarning levels or warning signals. Examples of downhole effects that maybe hazardous include stick-slip, whirl, or drill pipe bending, or otherart-recognized downhole effects.

Additionally, in certain embodiments with interrupt-style telemetry,combinations of downhole conditions may contribute collectively toincreased warning levels, for example a combination of relatively hightemperature, e.g., greater than 150 degrees Celsius, and relatively highrate and magnitude of shocks, e.g., 100 counts per second (cps) greaterthan 50 G, may indicate a more severe warning level than eithermeasurement alone. A time integration of said measurements may alsoindicate an increasing warning level, for instance, 20 Grms (root meansquare acceleration) of continuous vibration for a total of 100 hrs mayindicate a more severe warning level than for instance 20 Grms ofcontinuous vibration for a total of 10 hrs. As such, said warning levelsmay escalate over time. In one exemplary warning scheme, an integer maybe transmitted, for example, between 1 and 4 to indicate levels ofseverity, or more explicitly to indicate a recommended action such as tohalt drilling operations. Warning levels may be interpreted forintuitive purposes by a surface system to indicate, for instance, “red”,“yellow”, or “green” warning levels corresponding to for instance “haltdrilling”, “proceed with caution”, or “proceed normally” respectively.

Although exemplified herein for use in data logging for MWD/LWD, theMSID configured for data logging may be used in any harsh environment,e.g., downhole environments, where the ability to measure vibration andshock is beneficial, for instance in heavy manufacturing equipment,engine compartments of planes, cars, etc, or energy productionplants/turbines.

Moreover, while described herein using a circular housing embodiment,the MSID configured for data logging may also be used in any othershaped housing that would be sufficient for use in the tool string orthe collar of the drill string. For instance an ring-shaped circuitboard may be disposed in an annular cavity in a collar-mounted tool, aconventionally-shaped, e.g. rectangular, circuit board may be disposedin said cavity, in some instances axially. Said circuit boards, in someinstances, may comprise a modular bus or components thereof. Saidcircuit boards may be stacked, for instance ring-shaped circuit boardsmay be stacked in an annular cavity. An MSID disposed in a collar may beparticularly useful for accessing measurements helpful for determiningTOB and WOB, for instance by disposing at least on strain gauge on aportion of a collar mounted housing, and coupling said at least onestrain gauge to said MSID for measurement purposes.

i. Sensor Circuit Boards

The MSID of the present invention comprises one or more sensor circuitboards for measuring downhole conditions or orientation of the downholetools. Such circuit boards may include or couple to one or more of thefollowing components: at least one of an accelerometer, a magnetometer,a gyroscope, a temperature sensor, a pressure sensor, a strain gauge,useful for measuring a downhole condition or orientation of a downholetool, e.g., the toolstring or the drill bit.

In certain embodiments, the MSID is able to determine a rotational rateof a tool string about an axis.

In certain embodiments, the MSID is able to account for the effect ofgravity in some embodiments.

In certain embodiments, the MSID is able to account for the effect of“whirl,” which is art-recognized as lateral downhole vibration, in someembodiments.

Generally, both torsional acceleration and time-domain measurements ofdrill string rotation rate (RPMs) may indicate potentially hazardousdownhole effects such as stick slip and whirl. For instance, stick slip(i.e., a reaction to built up torsional energy along the length of thedrill string) may be measured by a time-varying and somewhat periodictorsional acceleration by way of a radially offset accelerometer with atleast one measurement axis having a component tangential to the toolstring or drill string. Alternatively, stick slip may be measured by atime-varying rotational rate (RPMs), for instance in a periodicallyvarying rotational rate. A rotational rate may be measured byaccelerometers configured to measure centripetal acceleration by way ofa radially offset accelerometer with at least one measurement axishaving a component radially to the tool string or drill string. Arotational rate may also be determined by an integration of torsionalacceleration. In some examples, mild stick slip may be indicated by avariation in rotational rate less than about the average rotational rateand may be termed moderate-to-pronounced torsional vibration in someinstances. In said examples, more sever stick slip may be indicated by avariation in rotational rate greater than about the average rotationalrate and may be termed significant to severe stick slip in someinstances. In some examples, the severity levels of stick slip and othereffects may simply be indicated by a level of torsional acceleration. Incertain embodiments herein, torsional acceleration may be determined byway of tangential acceleration measurements and/or centripetalacceleration measurements (the latter requiring the effect of atime-derivative to determine torsional acceleration).

In one embodiment of the invention, the MSID includes sensor circuitboards sufficient to measure accelerometer based vibration detectionand/or shock detection. In certain embodiments, the MSID sensor circuitboards are configured for detection of acceleration, e.g. shock andvibration, among 6 degrees of freedom. In certain embodiments, the MSIDsensor circuit boards are configured for detection of shock, e.g., withthe range of detectable shocks approximately less than about 1,000 G.

In certain embodiments, a sensor circuit board may comprise oneaccelerometer. In certain embodiments a sensor circuit board maycomprise multiple accelerometers.

In certain embodiments, the MSID comprises a combination of two sensorcircuit boards, wherein one sensor circuit board comprises oneaccelerometer, and the second sensor circuit board comprises twoaccelerometers. In a specific embodiment, 3 accelerometers may bearranged in accordance with FIG. 38B. This configuration of sensorcircuit boards makes available six degrees of freedom (6-DOF), which arecomposed of three translational (axial or lateral) degrees of freedom,(x, y, and z), and three rotational degrees of freedom (the rotationaround each of these axis, x_(r), y_(r), and z_(r)). Translationalacceleration can be measured by a single 3-axis accelerometer. In orderto measure the three degrees of rotational acceleration, a differencebetween two parallel axes of acceleration may be taken. FIG. 38B shows asample orientation suited for measuring 6-DOF.

Accordingly, in certain embodiments, a system of the present inventioncomprises a configuration of sensors providing for 6 degree of freedomacceleration measurements.

In certain embodiments, the MSID comprises at least one sensor circuitboard configured to measure rotation. FIG. 38B depicts that the rotationx_(r) may be found through the difference of the y vectors of A1 and A3;the rotation y_(r) may be found through the difference of the x vectorsof A1 and A3; and the rotation z_(r) may be found through the differencebetween the x acceleration vectors of A1 and A2. Furthermore, therotational velocity of a drill string around the central z axis isdirectly related to the centripetal acceleration. Centripetalacceleration may be measured by a sensor with at least one measurementaxis having a component directed radially, for instance, A3 in FIG. 38B.Another example configuration suited for determining rotational velocityby way of centripetal acceleration is shown in FIG. 38A. In FIG. 38A, aradial acceleration measurement may be taken as the difference betweenradial components of A1 and A2, as well as between the radial componentsof A1 and A3. The orthogonal placement and redundant radial measurementsenables separation of angular velocity around the z axis from the fouracceleration components while providing less measurement uncertainty.

As such, in one embodiment, the invention provides an MSID configuredfor data logging and/or reporting comprising a configuration ofaccelerometers in a 3-axis orientation, wherein this 3-axis orientationis comprised of a first sensor circuit board with at least oneaccelerometer electrically coupled to at least a second sensor circuitboard, e.g. comprising two accelerometers, wherein one of the said twoaccelerometers on said second board is axially aligned with anaccelerometer on the first sensor circuit board.

It may be generally advantageous to use different accelerometers tomeasure different accelerations, e.g. those used to measure rotationalvelocity, those used to measure vibration, and those used to measureshock. These three examples generally differ in drilling applications intheir typical ranges of acceleration, for instance, centripetalacceleration as may be used to determine rotational velocity may rangefrom about 0 to about 5 G, vibration whether it be translational orrotational may range from about 0 to about 50 G, and shock, whether itbe translational or rotational may range from about 0 to about severalthousand G. Generally acceleration measuring units, e.g. accelerometers,present tradeoffs between range and resolution, for instance anaccelerometer having a range of 1,000 G may have a resolution of about 5G, while an accelerometer having a range of 5 G may have a resolution ofabout 100 mG. Typically, measurements requiring higher range, also haverelaxed requirements on resolution. Additionally, variousaccelerometers, are characterized by various frequency response aspects,e.g. bandwidth specifications. As an example, vibration and shockmeasurements generally require moderate to high bandwidth, and moderateto high g accelerometers, and in particular shock measurements generallyrequire high bandwidth and high g accelerometers. On the other hand, RPMmeasurements generally require low g accelerometers and do not need highbandwidth. Low g accelerometers are useful in order to achieve highresolution analog-to-digital conversion across the expected range ofradial accelerations. Greater power efficiency and signal to noise ratiocan be achieved with low bandwidth accelerometers. A low g, lowbandwidth, but high resolution accelerometer useful for thesemeasurements is the Analog Devices Inc. part number AD22293Z. Meanwhilean accelerometer that presents a compromise between range and resolutionfor both shock and vibration is the Analog Devices Inc. part numberADXL377BCPZ-RL7. Analog Devices Inc. has offices Norwood, Mass. USA. Insummary, various accelerometers with various performance aspects may beemployed to measure the various quantities or effects described herein.In some cases, at least one accelerometer is “dual-used”, i.e. formeasuring more than one quantity or effect.

For clarity, torsional oscillation and stick slip refer to the conditionduring which the RPM of the BHA differ from the RPM at the surface andperiodically fluctuates between a maximum and a minimum value. In someexamples, the torsional oscillation and stick slip measurements may bereported based on Stick Slip Index (SSI), which is calculated based onthe equation: SSI=(Max RPM−Min RPM)/(2×Avg·RPM).

In certain embodiments, the sensor circuit board includes amagnetometer. Said magnetometer may be useful for among other things, todetermine a rate of rotation by way of a measuring a magneticorientation relative to earth's magnetic field and/or to aide in adetermination of direction, e.g., by providing a directional measurementwhich may be useful for among other things directional drillingoperations.

In certain embodiments an MSID may be used for directional measurements.Methods for converting measurements of acceleration in the presence ofgravity to directional measurements are well known in the industry. Insome instances a magnetometer aids those measurements. An example methodprovides for a directional measurement by way of coordinate systemaspects sometimes called pitch and roll estimation through rotationmatrices chosen to depend only on pitch and roll while the third degreeof freedom, sometimes called yaw, is left to be determined by way of amagnetometer configured to detect earth's magnetic field. Pitch, roll,and yaw are terms known in the industry, especially in avionics but morerecently in the context of handheld devices comprising accelerometersfor entertainment and the like. In some examples, a magnetometer mayreside elsewhere in a tool string or drill string and access to saidmagnetometer may be had by an MSID by way of a tool string or drillstring signal or data bus. In those examples, readings from saidmagnetometer may be used by an MSID for the purposes described above.

In certain embodiments, it may be useful to convert analog measurementsindicative of downhole conditions or orientation to digital signals, forinstance for recording in memory, for communicating the signals toanother digital system, for instance a tool string digital system by wayof a digital bus, and/or a digital telemetry system.

Due to the scarcity of power in downhole systems, in certainembodiments, power consumption is minimized. A variety of techniques maybe utilized to accomplish this minimization, including, but not limitedto designing based on the knowledge of expected signals. For example,some acceleration signals are typically wideband and/or continuous,e.g., “continuous vibration,” wherein an appropriate sampling rate ofthe acceleration signals can be selected to capture a substantial amountof the information therein, for example by setting the samplingfrequency to be more than twice as the highest frequency aspecttypically expected. Choosing a frequency substantially higher isgenerally expected to increase power consumption, e.g. beyond about 1-5mW, without providing for substantially more useful information. Anotherexample may involve temperature, which is expected to change slowly.Other examples include shock. Those acceleration signals typicallychange quickly and may be intermittent (as opposed to continuous).Generally the magnitude and rate of shocks are important. Moreover, theyare relatively short in duration, e.g. less than about 500 ms induration each. Reliable and accurate measurement of the importantfeatures of shocks requires a sample rate yielding several samples pershock, e.g. 100 samples. Sample rates of a single channel for shockmeasurement may be as high as about 50 or 100 ksps. However, due to theintermittency of some shock a continuously sampled signal, sampled at arelatively high rate, e.g. 100 ksps, is generally expected to increasepower consumption, e.g. beyond about 1-5 mW, without providing forsubstantially more useful information on average. One alternativesolution is to provide for an analog detection circuit, which may drawrelatively low power on average, e.g. less than 100 uW. An example ofsuch a circuit is a comparator configured to provide a signal transitionor a logic level signal when an acceleration beyond a predeterminedshock threshold, e.g. 20-50 G, is detected. Said signal transition oflogic level signal may be coupled to an input on a digital controllerand said digital controller may be configured to treat said signal as aninterrupt. In this way, high resolution or high speed sampling of therelevant acceleration signal may commence only when shocks are present,while power consumption of the full solution is generally expected to besubstantially less than full digital solutions.

Generally, an MSID should report a faithful representation of downholeconditions. Meanwhile, those downhole conditions may be damaging to theMSID itself—the MSID may be similar in construction to other componentsin the downhole system, the same components that the MSID's informationmay be useful for protecting. Therefore, it is desirable, in certainembodiments, that the MSID is protected from downhole conditions, but issimultaneously enabled to provide a faithful representations ofmonitored conditions. For example, downhole shock and vibration may bedamaging to systems including the MSID. The MSID may employ a body ofprotection features, for instance damped mechanical coupling betweenrelatively sensitive electronic components and the housing. Dampeningmay be provided for by way of encapsulant such as a potting compoundsurrounding said electronic components, or dampening pads or insertsdisposed between relatively hard surfaces of an electronics system and aportion of a housing or the like, or combinations thereof. Generallyprotection features may include dampening, mechanical energy dissipationand or soft coupling mechanisms. In certain embodiments, given an MSIDwith protection features such as those listed above, a faithfulrepresentation of downhole conditions can be recovered by providing fora pre-determined “map” between ambient conditions and measuredconditions. Said map may be measured, for example, in the form of atransfer function in the frequency domain, the transfer functiondescribing the gain and perhaps phase contribution of the protectionfeatures to the ambient excitation signal as measured by the MSID. Saidmap may be determined (calibrated) on the surface and then stored inmemory. Said map may be quantified for a variety of different operatingconditions, for instance at a variety of temperatures or pressures orimmersed in a variety of fluid types. Said map may be stored locally(e.g. in a memory on the MSID), or remotely (e.g. in a memory accessibleto a surface system). In the latter case, the MSID may be responsiblefor transmitting enough downhole parameters independent of theprotection features such that the surface system may map measuredconditions to downhole conditions.

Furthermore, logging, and in certain cases, reporting, may require amemory in one of the circuits of the MSID, e.g., on the sensor circuitboard. Both volatile and non-volatile memory may be employed for thesepurposes. In the case of volatile memory, a designer will enjoy a higherdensity of memory (more information may be stored in a comparable volumecompared to in non-volatile memory). However, volatile memory must besupported with a source of power in order to retain its stored data.Several solutions for using volatile memory downhole are possible,including, but not limited to utilizing a backup high temperatureprimary cell, e.g. a lithium thionyl chloride cell. Such a backup cellmay be an explicit cell within the housing of the system, for instance,a coin cell, or it may be shared in a larger system. A primary batteryavailable to the system may also be used for this purpose so long as aconnection to the primary battery may be maintained until memory can bedownloaded. In some instances, said primary battery can be a primarybattery otherwise used for power downhole or directional systems so longas the battery terminals are available to the system. In some instances,the battery terminals are available to the system by way of a drillsting or tool string electrical bus. An alternative solution may be toemploy high temperature rechargeable energy storage (HTRES) that ischarged before disconnection of the system from a power source. SaidHTRES may be charged by a downhole power source, e.g. a primary battery,generator or wireline connection. Said HTRES could provide enoughuseable energy to supply power to the volatile memory until memory canbe downloaded. For instance a high temperature 16 Megabit SRAM Partnumber TTS1MX16LVn3 available from TT semiconductor, Inc. Anaheim,Calif. USA requires about 6 mA of data retention current at about 2 V or12 mW of power. Therefore a HTRES having a stored energy of about 45Joules would be capable of providing power to said volatile memory fordata retention up to an hour. Examples of HTRES, includingultracapacitors described herein, are described below with respect tothe modular systems. However, said HTRES may be provided by way of aHigh temperature ultracapacitor available from FastCAP Systems Inc.Boston, Mass. USA with about 15-20 mL of volume. An alternative solutionwould combine an MSID with a power system comprising HTRES such as thoseavailable from FastCAP Systems Inc. Said HTRES may be charged by adownhole power source and provide for the data retention power followingdisconnection for a downhole power source until memory can bedownloaded. The SRAM above is available in a 52 pin package having anedge length of about one inch and a temperature rating of 200 degreesCelsius making it suitable for use in downhole tools such as an MSID.Non-volatile memory may also be employed, albeit generally at lowerdensities. For instance 1 Mbit EEPROM Part number TTE28HT010 availablefrom TT semiconductor may be employed. The EEPROM above is available inan LCC package having an edge length about one half of an inch and atemperature rating of 200 degrees Celsius making it suitable for use indownhole tools such as an MSID. Generally volatile memory may also havea limit on the number of write cycles (the number of times one can writeto memory) before it fails. Therefore, a designer may employ a scheme tobuffer memory, for instance in a volatile memory and then periodicallywrite that memory to a non-volatile memory.

In certain embodiments, certain monitoring data may be locally (e.g. ina memory on the MSID), and/or remotely (e.g. in a memory accessible to asurface system).

In certain embodiments, efficient use of memory capacity, e.g., in theMSID, is desirable. Any number of schemes for efficiently utilizing adownhole memory may be employed. In certain embodiments, the schemesgenerally employ a parameterization of the data that is recorded, forexample, instead of recording all of the temperature data in an intervalof one minute (a one minute window), the temperature data may berecorded over that minute in high resolution, for instance one sampleper second (1 sps) temporarily, and then the mean and standard deviationcomputed; then the mean and standard deviation may be stored instead ofthe raw temperature data. In this example, and for the purposes ofdefinition, the mean and standard deviation represent parameters of thedata and so we consider the above a method of parameterization of thedata. The result, in this example is that most of the meaningfulinformation is stored in a much smaller amount of memory, e.g., as 2bytes or pieces of data, as opposed to the larger amount of memory forthe entirety of the raw temperature data, e.g., 60 pieces of data.

In certain embodiments, the scheme for collecting and storing and/orparameterizing data may be informed by typical behavior relating to thesignal to be recorded. For instance, temperature generally varies slowlyin downhole environments and as the tool moves down the borehole. Incontrast, vibration may have high frequency content, however the averagepower in the frequency spectrum may not vary faster than a timescale ofabout a minute. Mechanical shock on the other hand tends to beintermittent, short duration, and requires high resolution during theshock event to accurately measure its salient features. An example of ashock and vibration logging scheme includes vibration loggingparameterized by mean and standard deviation once per minute (1 spm) foreach axis, shock count, peak shock magnitude and average shock magnitudeparameterized at 1 spm; temperature averaged once every ten minutes (0.1spm), stick slip index mean, standard deviation and peak, averaged at 1spm, rotational rate (RPMs) averaged at 1 spm. Based on the number ofmeasured quantities and their relative importance to the designer oruser, the desired record length, and the amount of available memory, thelogging scheme may be adjusted, for example even by the user. Resolutionof the various quantities may be subject to trade off for longer recordlengths and/or more resolution in measurement of other quantities.

In certain embodiments, the sensor circuit board may comprise a circuitboard configured to receive data from sensors outside the MSID, e.g.,from strain gauges, temperature sensors, or annular pressure, e.g.,mounted along with the housing containing the MSID.

Accordingly, in one embodiment, the sensor circuit board is configuredto determine torque on bit (TOB) by receiving data from one or morestrain gauges coupled to the toolstring. A collar-mounted version of thesystem, in certain embodiments, may simplify the coupling to the drillstring. In certain embodiments, a strain gauge may be mounted so thatits major axis is not aligned with the circumference of a drill stringhousing, such that the gauge is able to indicate a “twisting” of thedrill string housing, e.g., by way of a change in its resistance.

In another embodiment, the sensor circuit board is configured todetermine weight on bit (WOB) by receiving data from one or more straingauges coupled to the toolstring. In certain embodiments, a strain gaugemay be mounted so that its major axis is substantially aligned with themajor axis of the drill string, such that the gauge is able to indicatea compression of the drill string housing by way of a change in itsresistance.

In another embodiment, the sensor circuit board is configured todetermine temperature by way of a temperature sensor, by receiving datafrom a resistance temperature detector (RTD) which indicates atemperature by way of changing resistance.Said changes in variable resistance above, (as in strain gauge or as inRTD cases) may be measured in any number of ways, but one exampleincludes providing for a fixed resistance in series with the straingauge or the RTD the combination connected to a reference voltage andground. The node at the connection between the fixed resistance and thevariable resistance will provide for a voltage indicative of thevariable resistance. For example, as the strain gauge resistancedecreases, said voltage will decrease. In some examples, it is thenuseful to read said voltage to a digital controller by way of an analogto digital conversion.

Ultracapacitors

Further disclosed herein are capacitors for use the present inventionthat provide users with improved performance in a wide range oftemperatures. Such ultracapacitors may comprise an energy storage celland an electrolyte system within an hermetically sealed housing, thecell electrically coupled to a positive contact and a negative contact,wherein the ultracapacitor is configured to operate at a temperaturewithin a temperature range between about −40 degrees Celsius to about210 degrees Celsius. For example, the capacitors for use in the presentinvention may comprise advanced electrolyte systems described herein,and may be operable at temperatures ranging from about as low as minus40 degrees Celsius to as high as about 210 degrees Celsius. Suchcapacitors shall be described herein with reference to FIG. 3.

In general, the capacitor of the present invention includes energystorage media that is adapted for providing a combination of highreliability, wide operating temperature range, high power density andhigh energy density when compared to prior art devices. The capacitorincludes components that are configured to ensure operation over thetemperature range, and includes electrolytes 6 that are selected, e.g.,from known electrolyte systems or from the advanced electrolyte systemsdescribed herein. The combination of construction, energy storage mediaand electrolyte systems described herein provide the robust capacitorsfor use in the present invention that afford operation under extremeconditions with enhanced properties over existing capacitors, and withgreater performance and durability.

Accordingly, the present invention may comprise an ultracapacitorcomprising: an energy storage cell and an advanced electrolyte system(AES) within an hermetically sealed housing, the cell electricallycoupled to a positive contact and a negative contact, wherein theultracapacitor is configured to operate at a temperature within atemperature range (“operating temperature”) between about −40 degreesCelsius to about 210 degrees Celsius; about −35 degrees Celsius to about210 degrees Celsius; about −40 degrees Celsius to about 205 degreesCelsius; about −30 degrees Celsius to about 210 degrees Celsius; about−40 degrees Celsius to about 200 degrees Celsius; about −25 degreesCelsius to about 210 degrees Celsius; about −40 degrees Celsius to about195 degrees Celsius; about −20 degrees Celsius to about 210 degreesCelsius; about −40 degrees Celsius to about 190 degrees Celsius; about−15 degrees Celsius to about 210 degrees Celsius; about −40 degreesCelsius to about 185 degrees Celsius; about −10 degrees Celsius to about210 degrees Celsius; about −40 degrees Celsius to about 180 degreesCelsius; about −5 degrees Celsius to about 210 degrees Celsius; about−40 degrees Celsius to about 175 degrees Celsius; about 0 degreesCelsius to about 210 degrees Celsius; about −40 degrees Celsius to about170 degrees Celsius; about 5 degrees Celsius to about 210 degreesCelsius; about −40 degrees Celsius to about 165 degrees Celsius; about10 degrees Celsius to about 210 degrees Celsius; about −40 degreesCelsius to about 160 degrees Celsius; about 15 degrees Celsius to about210 degrees Celsius; about −40 degrees Celsius to about 155 degreesCelsius; about 20 degrees Celsius to about 210 degrees Celsius; about−40 degrees Celsius to about 150 degrees Celsius.

For example, as shown in FIG. 3, an exemplary embodiment of a capacitoris shown. In this case, the capacitor is an “ultracapacitor 10.” Theexemplary ultracapacitor 10 is an electric double-layer capacitor(EDLC). The ultracapacitor 10 may be embodied in several different formfactors (i.e., exhibit a certain appearance). Examples of potentiallyuseful form factors include a cylindrical cell, an annular orring-shaped cell, a flat prismatic cell or a stack of flat prismaticcells comprising a box-like cell, and a flat prismatic cell that isshaped to accommodate a particular geometry such as a curved space. Acylindrical form factor may be most useful in conjunction with acylindrical system or a system mounted in a cylindrical form factor orhaving a cylindrical cavity. An annular or ring-shaped form factor maybe most useful in conjunction with a system that is ring-shaped ormounted in a ring-shaped form factor or having a ring-shaped cavity. Aflat prismatic form factor may be most useful in conjunction with asystem that is rectangularly-shaped, or mounted in arectangularly-shaped form factor or having a rectangularly-shapedcavity.

While generally disclosed herein in terms of a “jelly roll” application(i.e., a storage cell 12 that is configured for a cylindrically shapedhousing 7), the rolled storage cell 23 (referring to FIG. 25) may takeany form desired. For example, as opposed to rolling the storage cell12, folding of the storage cell 12 may be performed to provide for therolled storage cell 23. Other types of assembly may be used. As oneexample, the storage cell 12 may be a flat cell, referred to as a cointype, pouch type, or prismatic type of cell. Accordingly, rolling ismerely one option for assembly of the rolled storage cell 23. Therefore,although discussed herein in terms of being a “rolled storage cell 23”,this is not limiting. It may be considered that the term “rolled storagecell 23” generally includes any appropriate form of packaging or packingthe storage cell 12 to fit well within a given design of the housing 7.

Various forms of the ultracapacitor 10 may be joined together. Thevarious forms may be joined using known techniques, such as weldingcontacts together, by use of at least one mechanical connector, byplacing contacts in electrical contact with each other and the like. Aplurality of the ultracapacitors 10 may be electrically connected in atleast one of a parallel and a series fashion.

For the purposes of this invention, an ultracapacitor 10 may have avolume in the range from about 0.05 cc to about 7.5 liters.

The components of the ultracapacitors of the present invention will nowbe discussed, in turn.

Electrolyte Systems

Electrolytes

The electrolyte 6 includes a pairing of cations 9 and anions 11 and mayinclude a solvent. The electrolyte 6 may be referred to as an “ionicliquid” as appropriate. Various combinations of cations 9, anions 11 andsolvent may be used. In the exemplary ultracapacitor 10, the cations 9may include at least one of 1-(3-Cyanopropyl)-3-methylimidazolium,1,2-Dimethyl-3-propylimidazolium, 1,3-Bis(3-cyanopropyl)imidazolium,1,3-Diethoxyimidazolium, 1-Butyl-1-methylpiperidinium,1-Butyl-2,3-dimethylimidazolium, 1-Butyl-3-methylimidazolium,1-Butyl-4-methylpyridinium, 1-Butylpyridinium,1-Decyl-3-methylimidazolium, 1-Ethyl-3-methylimidazolium,3-Methyl-1-propylpyridinium, and combinations thereof as well as otherequivalents as deemed appropriate. Additional exemplary cations 9include imidazolium, pyrazinium, piperidinium, pyridinium, pyrimidinium,and pyrrolidinium (structures of which are depicted in FIG. 4). In theexemplary ultracapacitor 10, the anions 11 may include at least one ofbis(trifluoromethanesulfonate)imide,tris(trifluoromethanesulfonate)methide, dicyanamide, tetrafluoroborate,hexafluorophosphate, trifluoromethanesulfonate,bis(pentafluoroethanesulfonate)imide, thiocyanate,trifluoro(trifluoromethyl)borate, and combinations thereof as well asother equivalents as deemed appropriate.

The solvent may include acetonitrile, amides, benzonitrile,butyrolactone, cyclic ether, dibutyl carbonate, diethyl carbonate,diethylether, dimethoxyethane, dimethyl carbonate, dimethylformamide,dimethylsulfone, dioxane, dioxolane, ethyl formate, ethylene carbonate,ethylmethyl carbonate, lactone, linear ether, methyl formate, methylpropionate, methyltetrahydrofuran, nitrile, nitrobenzene, nitromethane,n-methylpyrrolidone, propylene carbonate, sulfolane, sulfone,tetrahydrofuran, tetramethylene sulfone, thiophene, ethylene glycol,diethylene glycol, triethylene glycol, polyethylene glycols, carbonicacid ester, ã-butyrolactone, nitrile, tricyanohexane, any combinationthereof or other material(s) that exhibit appropriate performancecharacteristics.

Referring now to FIG. 4, there are shown various additional embodimentsof cations 9 suited for use in an ionic liquid to provide theelectrolyte 6. These cations 9 may be used alone or in combination witheach other, in combination with at least some of the foregoingembodiments of cations 9, and may also be used in combination with othercations 9 that are deemed compatible and appropriate by a user,designer, manufacturer or other similarly interested party. The cations9 depicted in FIG. 4 include, without limitation, ammonium, imidazolium,oxazolium, phosphonium, piperidinium, pyrazinium, pyrazinium,pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, sulfonium,thiazolium, triazolium, guanidium, isoquinolinium, benzotriazolium,viologen-types, and functionalized imidazolium cations.

With regard to the cations 9 shown in FIG. 4, various branch groups (R₁,R₂, R₃, . . . R_(x)) are included. In the case of the cations 9, eachbranch groups (R_(x)) may be one of alkyl, heteroalkyl, alkenyl,heteroalkenyl, alkynyl, heteroalkynyl, halo, amino, nitro, cyano,hydroxyl, sulfate, sulfonate, or a carbonyl group any of which isoptionally substituted.

Generally, any ion with a negative charge maybe used as the anion 11.The anion 11 selected is generally paired with a large organic cation 9to form a low temperature melting ionic salt. Room temperature (andlower) melting salts come from mainly large anions 9 with a charge of−1. Salts that melt at even lower temperatures generally are realizedwith anions 11 with easily delocalized electrons. Anything that willdecrease the affinity between ions (distance, delocalization of charge)will subsequently decrease the melting point. Although possible anionformations are virtually infinite, only a subset of these will work inlow temperature ionic liquid application. This is a non-limitingoverview of possible anion formations for ionic liquids.

Common substitute groups (a) suited for use of the anions 11 provided inTable 6 include: —F⁻, —Cl⁻, —Br⁻, —I⁻, —OCH₃ ⁻, —CN⁻, —SCN⁻, —C₂H₃O₂ ⁻,—ClO⁻, —ClO₂ ⁻, —ClO₃ ⁻, —ClO₄ ⁻, —NCO⁻, —NCS⁻, —NCSe⁻, —NCN⁻,—OCH(CH₃)₂ ⁻, —CH₂OCH₃ ⁻, —COOH⁻, —OH⁻, —SOCH₃ ⁻, —SO₂CH₃ ⁻, —SOCH₃ ⁻,—SO₂CF₃ ⁻, —SO₃H⁻, —SO₃CF₃ ⁻, —O(CF₃)₂C₂(CF₃)₂O⁻, —CF₃ ⁻, —CHF₂ ⁻,—CH₂F⁻, —CH₃ ⁻—NO₃ ⁻, —NO₂ ⁻, —SO₃ ⁻, —SO₄ ²⁻, —SF₅ ⁻, —CB₁₁H₁₂ ⁻,—CB₁₁H₆C_(l6) ⁻, —CH₃CB₁₁H₁₁ ⁻, —C₂H₅CB₁₁H₁₁ ⁻, -A-PO₄ ⁻, -A-SO₂ ⁻,A-SO₃ ⁻, -A-SO₃H⁻, -A-COO⁻, -A-CO⁻ {where A is a phenyl (the phenylgroup or phenyl ring is a cyclic group of atoms with the formula C₆H₅)or substituted phenyl, alkyl, (a radical that has the general formulaCnH_(2n+1), formed by removing a hydrogen atom from an alkane) orsubstituted alkyl group, negatively charged radical alkanes, (alkane arechemical compounds that consist only of hydrogen and carbon atoms andare bonded exclusively by single bonds) halogenated alkanes and ethers(which are a class of organic compounds that contain an oxygen atomconnected to two alkyl or aryl groups).

With regard to anions 11 suited for use in an ionic liquid that providesthe electrolyte 6, various organic anions 11 may be used. Exemplaryanions 11 and structures thereof are provided in Table 6. In a firstembodiment, (No. 1), exemplary anions 11 are formulated from the list ofsubstitute groups (á) provided above, or their equivalent. In additionalembodiments, (Nos. 2-5), exemplary anions 11 are formulated from arespective base structure (Y₂, Y₃, Y₄, . . . Y_(n)) and a respectivenumber of anion substitute groups (á₁, á₂, á₃, . . . á_(n)), where therespective number of anion substitute groups (á) may be selected fromthe list of substitute (á) groups provided above, or their equivalent.Note that in some embodiments, a plurality of anion substitute groups(á) (i.e., at least one differing anion substitute group (á)) may beused in any one embodiment of the anion 11. Also, note that in someembodiments, the base structure (Y) is a single atom or a designatedmolecule (as described in Table 6), or may be an equivalent.

More specifically, and by way of example, with regard to the exemplaryanions provided in Table 6, certain combinations may be realized. As oneexample, in the case of No. 2, the base structure (Y₂) includes a singlestructure (e.g., an atom, or a molecule) that is bonded to two anionsubstitute groups (á₂). While shown as having two identical anionsubstitute groups (á₂), this need not be the case. That is, the basestructure (Y₂) may be bonded to varying anion substitute groups (á₂),such as any of the anion substitute groups (á) listed above. Similarly,the base structure (Y₃) includes a single structure (e.g., an atom) thatis bonded to three anion substitute groups (á₃), as shown in case No. 3.Again, each of the anion substitute groups (á) included in the anion maybe varied or diverse, and need not repeat (be repetitive or besymmetric) as shown in Table 6. In general, with regard to the notationin Table 6, a subscript on one of the base structures denotes a numberof bonds that the respective base structure may have with anionsubstitute groups (á). That is, the subscript on the respective basestructure (Y_(n)) denotes a number of accompanying anion substitutegroups (á_(n)) in the respective anion.

TABLE 6 Exemplary Organic Anions for an Ionic Liquid No.: Ion Guidelinesfor Anion Structure and Exemplary Ionic Liquids 1 —á₁ Some of the aboveá may mix with organic cations to form an ionic liquid. An exemplaryanion: Cl⁻ Exemplary ionic liquid: [BMI*][Cl] *BMI - butyl methylimidazolium 2 —Y₂á₂ Y₂ may be any of the following: N, O, C═O, S═O.Exemplary anions include: B (CF₃C0₂)₄ ⁻N(SO₂CF₃)₂ ⁻ Exemplary ionicliquid: [EMI*][NTF₂] *EMI - ethyl methyl imidazolium 3 —Y₃á₃ Y₃ may beany of the following: Be, C, N, O, Mg, Ca, Ba, Ra, Au. Exemplary anionsinclude: —C(SO₂CF₃)₃ ⁻ Exemplary ionic liquid: [BMI] C(SO₂CF₃)₃ ⁻ 4—Y₄á₄ Y₄ may be any of the following: B, Al, Ga, Th, In, P. Exemplaryanions include: —BF₄ ⁻, —AlCl₄ ⁻ Exemplary ionic liquid: [BMI][BF₄] 5—Y₆á₆ Y₆ can be any of the following: P, S, Sb, As, N, Bi, Nb, Sb.Exemplary anions include: —P(CF₃)₄F₂ ⁻, —AsF₆ ⁻ Exemplary ionic liquid:[BMI][PF₆]

Advanced Electrolyte Systems of the Invention

The advanced electrolyte systems that may be used in the capacitors ofthe present invention provide the electrolyte component of theultracapacitors of the present invention, and are noted as “electrolyte6” in FIG. 3. The electrolyte 6 fills void spaces in and between theelectrode 3 and the separator 5. In general, the advanced electrolytesystems of the invention comprise unique electrolytes, purified enhancedelectrolytes, or combinations thereof, wherein the electrolyte 6 is asubstance, e.g., comprised of one or more salts or ionic liquids, whichdisassociate into electrically charged ions (i.e., positively chargedcations and negatively charged anions) and may include a solvent. In theadvanced electrolyte systems of the present invention, such electrolytecomponents are selected based on the enhancement of certain performanceand durability characteristics, and may be combined with one or moresolvents, which dissolve the substance to generate compositions withnovel and useful electrochemical stability and performance.

The advanced electrolyte systems that may be used in the capacitors ofthe present invention afford unique and distinct advantages to theultracapacitors over existing energy storage devices (e.g., energystorage devices containing electrolytes not disclosed herein, or energystorage devices containing electrolytes having insufficient purity).These advantages include improvements in both performance and durabilitycharacteristics, such as one or more of the following: decreased totalresistance, increased long-term stability of resistance (e.g., reductionin increased resistance of material over time at a given temperature),increased total capacitance, increased long-term stability ofcapacitance (e.g. reduction in decreased capacitance of a capacitor overtime at a given temperature), increased energy density (e.g. bysupporting a higher voltage and/or by leading to a higher capacitance),increased voltage stability, reduced vapor pressure, wider temperaturerange performance for an individual capacitor (e.g. without asignificant drop in capacitance and/or increase in ESR whentransitioning between two temperatures, e.g. without more than a 90%decrease in capacitance and/or a 1000% increase in ESR whentransitioning from about +30° C. to about −40° C.), increasedtemperature durability for an individual capacitor (e.g., less than a50% decrease in capacitance at a given temperature after a given timeand/or less than a 100% increase in ESR at a given temperature after agiven time, and/or less than 10 A/L of leakage current at a giventemperature after a given time, e.g., less than a 40% decrease incapacitance and/or a 75% increase in ESR, and/or less than 5 A/L ofleakage current, e.g., less than a 30% decrease in capacitance and/or a50% increase in ESR, and/or less than 1 A/L of leakage current);increased ease of manufacturability (e.g. by having a reduced vaporpressure, and therefore better yield and/or more efficient methods offilling a capacitor with electrolyte), and improved cost effectiveness(e.g. by filling void space with material that is less costly thananother material). For clarity, performance characteristics relate tothe properties directed to utility of the device at a given point of usesuitable for comparison among materials at a similar given point of use,while durability characteristics relate to properties directed toability to maintain such properties over time. The performance anddurability examples above should serve to provide context for what areconsidered “significant changes in performance or durability” herein.

The properties of the AES, or Electrolyte 6, may be the result ofimprovements in properties selected from increases in capacitance,reductions in equivalent-series-resistance (ESR), high thermalstability, a low glass transition temperature (Tg), an improvedviscosity, a particular rheopectic or thixotropic property (e.g., onethat is dependent upon temperature), as well as high conductivity andexhibited good electric performance over a wide range of temperatures.As examples, the electrolyte 6 may have a high degree of fluidicity, or,in contrast, be substantially solid, such that separation of electrode 3is assured.

The advanced electrolyte systems of the present invention include, novelelectrolytes described herein for use in high temperatureultracapacitors, highly purified electrolytes for use in hightemperature ultracapacitors, and enhanced electrolyte combinationssuitable for use in temperature ranges from −40 degrees Celsius to 210degrees Celsius, without a significant drop in performance or durabilityacross all temperatures.

In one particular embodiment, the AES comprises a novel electrolyteentity (NEE), e.g., wherein the NEE is adapted for use in hightemperature ultracapacitors. In certain embodiments, the ultracapacitoris configured to operate at a temperature within a temperature rangebetween about 80 degrees Celsius to about 210 degrees Celsius, e.g., atemperature range between about 80 degrees Celsius to about 150 degreesCelsius.

In one particular embodiment, the AES comprises a highly purifiedelectrolyte, e.g., wherein the highly purified electrolyte is adaptedfor use in high temperature ultracapacitors. In certain embodiments, theultracapacitor is configured to operate at a temperature within atemperature range between about 80 degrees Celsius to about 210 degreesCelsius.

In one particular embodiment, the AES comprises an enhanced electrolytecombination, e.g., wherein the enhanced electrolyte combination isadapted for use in both high and low temperature ultracapacitors. Incertain embodiments, the ultracapacitor is configured to operate at atemperature within a temperature range between about −40 degrees Celsiusto about 150 degrees Celsius.

As such, and as noted above, the advantages over the existingelectrolytes of known energy storage devices are selected from one ormore of the following improvements: decreased total resistance,increased long-term stability of resistance, increased totalcapacitance, increased long-term stability of capacitance, increasedenergy density, increased voltage stability, reduced vapor pressure,wider temperature range performance for an individual capacitor,increased temperature durability for an individual capacitor, increasedease of manufacturability, and improved cost effectiveness.

In certain embodiments of the ultracapacitor, the energy storage cellcomprises a positive electrode and a negative electrode.

In certain embodiments of the ultracapacitor, at least one of theelectrodes comprises a carbonaceous energy storage media, e.g., whereinthe carbonaceous energy storage media comprises carbon nanotubes. Inparticular embodiments, the carbonaceous energy storage media maycomprise at least one of activated carbon, carbon fibers, rayon,graphene, aerogel, carbon cloth, and carbon nanotubes.

In certain embodiments of the ultracapacitor, each electrode comprises acurrent collector.

In certain embodiments of the ultracapacitor, the AES is purified toreduce impurity content. In certain embodiments of the ultracapacitor,the content of halide ions in the electrolyte is less than about 1,000parts per million, e.g., less than about 500 parts per million, e.g.,less than about 100 parts per million, e.g., less than about 50 partsper million. In a particular embodiment, the halide ion in theelectrolyte is selected from one or more of the halide ions selectedfrom the group consisting of chloride, bromide, fluoride and iodide. Inparticular embodiments, the total concentration of impurities in theelectrolyte is less than about 1,000 parts per million. In certainembodiments, the impurities are selected from one or more of the groupconsisting of bromoethane, chloroethane, 1-bromobutane, 1-chlorobutane,1-methylimidazole, ethyl acetate and methylene chloride.

In certain embodiments of the ultracapacitor, the total concentration ofmetallic species in the electrolyte is less than about 1,000 parts permillion. In a particular embodiment, the metallic species is selectedfrom one or more metals selected from the group consisting of Cd, Co,Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb, and Zn. In another particularembodiment, the metallic species is selected from one or more alloys ofmetals selected from the group consisting of Cd, Co, Cr, Cu, Fe, K, Li,Mo, Na, Ni, Pb, and Zn. In yet another particular embodiment, themetallic species is selected from one or more oxides of metals selectedfrom the group consisting of Cd, Co, Cr, Cu, Fe, K, Li, Mo, Na, Ni, Pb,and Zn.

In certain embodiments of the ultracapacitor, the total water content inthe electrolyte is less than about 500 parts per million, e.g., lessthan about 100 parts per million, e.g., less than about 50 parts permillion, e.g., about 20 parts per million.

In certain embodiments of the ultracapacitor, the housing comprises abarrier disposed over a substantial portion of interior surfacesthereof. In particular embodiments, the barrier comprises at least oneof polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinatedethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE). Inparticular embodiments, the barrier comprises a ceramic material. Thebarrier may also comprise a material that exhibits corrosion resistance,a desired dielectric property, and a low electrochemical reactivity. Ina specific embodiment of the barrier, the barrier comprises multiplelayers of materials.

In certain embodiments of the ultracapacitor, the housing comprises amultilayer material, e.g., wherein the multilayer material comprises afirst material clad onto a second material. In a particular embodiment,the multilayer material comprises at least one of steel, tantalum andaluminum.

In certain embodiments of the ultracapacitor, the housing comprises atleast one hemispheric seal.

In certain embodiments of the ultracapacitor, the housing comprises atleast one glass-to-metal seal, e.g., wherein a pin of the glass-to-metalseal provides one of the contacts. In a particular embodiment, theglass-to-metal seal comprises a feed-through that is comprised of amaterial selected from the group consisting of an iron-nickel-cobaltalloy, a nickel iron alloy, tantalum, molybdenum, niobium, tungsten, anda form of stainless and titanium. In another particular embodiment, theglass-to-metal seal comprises a body that is comprised of at least onematerial selected from the group consisting of nickel, molybdenum,chromium, cobalt, iron, copper, manganese, titanium, zirconium,aluminum, carbon, and tungsten and an alloy thereof.

In certain embodiments of the ultracapacitor, the energy storage cellcomprises a separator to provide electrical separation between apositive electrode and a negative electrode, e.g., wherein the separatorcomprises a material selected from the group consisting of polyamide,polytetrafluoroethylene (PTFE), polyether ether ketone (PEEK), aluminumoxide (Al₂O₃), fiberglass, fiberglass reinforced plastic, or anycombination thereof. In a particular embodiment, the separator issubstantially free of moisture. In another particular embodiment, theseparator is substantially hydrophobic.

In certain embodiments of the ultracapacitor, the hermetic seal exhibitsa leak rate that is no greater than about 5.0×10⁻⁶ atm-cc/sec, e.g., nogreater than about 5.0×10⁻⁷ atm-cc/sec, e.g., no greater than about5.0×10⁻⁸ atm-cc/sec, e.g., no greater than about 5.0×10⁻⁹ atm-cc/sec,e.g., no greater than about 5.0×10⁻¹⁰ atm-cc/sec.

In certain embodiments of the ultracapacitor, at least one contact isconfigured for mating with another contact of another ultracapacitor.

In certain embodiments of the ultracapacitor, the storage cell comprisesa wrapper disposed over an exterior thereof, e.g., wherein the wrappercomprises one of PTFE and polyimide.

In certain embodiments of the ultracapacitor, a volumetric leakagecurrent is less than about 10 Amperes per Liter within the temperaturerange.

In certain embodiments of the ultracapacitor, a volumetric leakagecurrent is less than about 10 Amperes per Liter over a specified voltagerange between about 0 Volts and about 4 Volts, e.g. between about 0Volts and about 3 Volts, e.g. between about 0 Volts and about 2 Volts,e.g. between about 0 Volts and about 1 Volt. In certain embodiments ofthe ultracapacitor, the level of moisture within the housing is lessthan about 1,000 parts per million (ppm), e.g., less than about 500parts per million (ppm), e.g., less than about 350 parts per million(ppm).

In certain embodiments of the ultracapacitor, the moisture content in anelectrode of the ultracapacitor that is less than about 1,000 ppm, e.g.,less than about 500 ppm, e.g., less than about 350 parts per million(ppm).

In certain embodiments of the ultracapacitor, the moisture content in aseparator of the ultracapacitor that is less than about 1,000 ppm, e.g.,less than about 500 ppm, e.g., less than about 160 parts per million(ppm).

In certain embodiments of the ultracapacitor, the chloride content isless than about 300 ppm for one of the components selected from thegroup consisting of an electrode, electrolyte and a separator.

In certain embodiments of the ultracapacitor, the volumetric leakagecurrent (mA/cc) of the ultracapacitor is less than about 10 mA/cc whileheld at the substantially constant temperature, e.g., less than about 1mA/cc while held at the substantially constant temperature. In aparticular embodiment,

In certain embodiments of the ultracapacitor, the volumetric leakagecurrent of the ultracapacitor is greater than about 0.0001 mA/cc whileheld at the substantially constant temperature.

In certain embodiments of the ultracapacitor, volumetric capacitance ofthe ultracapacitor is between about 6 F/cc and about 1 mF/cc; betweenabout 10 F/cc and about 5 F/cc; or between about 50 F/cc and about 8F/cc.

In certain embodiments of the ultracapacitor, the volumetric ESR of theultracapacitor is between about 20 mOhms·cc and 200 mOhms·cc; betweenabout 150 mOhms·cc and 2 Ohms·cc; between about 1.5 Ohms·cc and 200Ohms·cc; or between about 150 Ohms·cc and 2000 Ohms·cc.

In certain embodiments of the ultracapacitor, the ultracapacitorexhibits a capacitance decrease less than about 90 percent while held ata substantially constant voltage and operating temperature. In aparticular embodiment, the ultracapacitor exhibits a capacitancedecrease less than about 90 percent while held at a substantiallyconstant voltage and operating temperature for at least 1 hour, e.g. forat least 10 hours, e.g. for at least 50 hours, e.g. for at least 100hours, e.g. for at least 200 hours, e.g. for at least 300 hours, e.g.for at least 400 hours, e.g. for at least 500 hours, e.g. for at least1,000 hours.

In certain embodiments of the ultracapacitor, the ultracapacitorexhibits an ESR increase less than about 1,000 percent while held at asubstantially constant voltage and operating temperature for at least 1hour, e.g. for at least 10 hours, e.g. for at least 50 hours, e.g. forat least 100 hours, e.g. for at least 200 hours, e.g. for at least 300hours, e.g. for at least 400 hours, e.g. for at least 500 hours, e.g.for at least 1,000 hours.

Novel Electrolyte Entities (NEE)

The advanced electrolyte systems (AES) of the present inventioncomprise, in one embodiment, certain novel electrolytes for use in hightemperature ultracapacitors. In this respect, it has been found thatmaintaining purity and low moisture relates to a degree of performanceof the energy storage 30; and that the use of electrolytes that containhydrophobic materials and which have been found to demonstrate greaterpurity and lower moisture content are advantageous for obtainingimproved performance. These electrolytes exhibit good performancecharacteristics in a temperature range of about 80 degrees Celsius toabout 210 degrees Celsius, e.g., about 80 degrees Celsius to about 200degrees Celsius, e.g., about 80 degrees Celsius to about 190 degreesCelsius e.g., about 80 degrees Celsius to about 180 degrees Celsiuse.g., about 80 degrees Celsius to about 170 degrees Celsius e.g., about80 degrees Celsius to about 160 degrees Celsius e.g., about 80 degreesCelsius to about 150 degrees Celsius e.g., about 85 degrees Celsius toabout 145 degrees Celsius e.g., about 90 degrees Celsius to about 140degrees Celsius e.g., about 95 degrees Celsius to about 135 degreesCelsius e.g., about 100 degrees Celsius to about 130 degrees Celsiuse.g., about 105 degrees Celsius to about 125 degrees Celsius e.g., about110 degrees Celsius to about 120 degrees Celsius.

Accordingly, novel electrolyte entities useful as the advancedelectrolyte system (AES) include species comprising a cation (e.g.,cations shown in FIG. 4 and described herein) and an anion, orcombinations of such species. In some embodiments, the species comprisesa nitrogen-containing, oxygen-containing, phosphorus-containing, and/orsulfur-containing cation, including heteroaryl and heterocyclic cations.In one set of embodiments, the advanced electrolyte system (AES) includespecies comprising a cation selected from the group consisting ofammonium, imidazolium, oxazolium, phosphonium, piperidinium, pyrazinium,pyrazolium, pyridazinium, pyridinium, pyrimidinium, sulfonium,thiazolium, triazolium, guanidium, isoquinolinium, benzotriazolium, andviologen-type cations, any of which may be substituted with substituentsas described herein. In one embodiment, the novel electrolyte entitiesuseful for the advanced electrolyte system (AES) of the presentinvention include any combination of cations presented in FIG. 4,selected from the group consisting of phosphonium, piperidinium, andammonium, wherein the various branch groups R_(x) (e.g., R₁, R₂, R₃, . .. R_(x)) may be selected from the group consisting of alkyl,heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, halo,amino, nitro, cyano, hydroxyl, sulfate, sulfonate, and carbonyl, any ofwhich is optionally substituted, and wherein at least two R_(x) are notH (i.e., such that the selection and orientation of the R groups producethe cationic species shown in FIG. 4); and the anion selected from thegroup consisting of tetrafluoroborate,bis(trifluoromethylsulfonyl)imide, tetracyanoborate, andtrifluoromethanesulfonate.

For example, given the combinations of cations and anions above, in aparticular embodiment, the AES may be selected from the group consistingof trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide,1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, andbutyltrimethylammonium bis(trifluoromethylsulfonyl)imide. Datasupporting the enhanced performance characteristics in a temperaturerange as demonstrated through Capacitance and ESR measurements overtime, indicate high temperature utility and long term durability.

In certain embodiments, the AES is trihexyltetradecylphosphoniumbis(trifluoromethylsulfonyl)imide.

In certain embodiments, the AES is 1-butyl-1-methylpiperidiniumbis(trifluoromethylsulfonyl)imide.

In certain embodiments, the AES is butyltrimethylammoniumbis(trifluoromethylsulfonyl)imide.

In another embodiment, the novel electrolyte entities useful for theadvanced electrolyte system (AES) of the present invention include anycombination of cations presented in FIG. 4, selected from the groupconsisting of imidazolium and pyrrolidinium, wherein the various branchgroups R_(x) (e.g., R₁, R₂, R₃, . . . R_(x)) may be selected from thegroup consisting of alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl,heteroalkynyl, halo, amino, nitro, cyano, hydroxyl, sulfate, sulfonate,and carbonyl, any of which is optionally substituted, and wherein atleast two R_(x) are not H (i.e., such that the selection and orientationof the R groups produce the cationic species shown in FIG. 4); and theanion selected from the group consisting of tetrafluoroborate,bis(trifluoromethylsulfonyl)imide, tetracyanoborate, andtrifluoromethanesulfonate. In one particular embodiment, the two R_(x)that are not H, are alkyl. Moreover, the noted cations exhibit highthermal stability, as well as high conductivity and exhibit goodelectrochemical performance over a wide range of temperatures.

For example, given the combinations of cations and anions above, in aparticular embodiment, the AES may be selected from the group consistingof 1-butyl-3-methylimidazolium tetrafluoroborate;1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium tetrafluoroborate;1-ethyl-3-methylimidazolium tetracyanoborate;1-hexyl-3-methylimidazolium tetracyanoborate;1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide;1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate;1-butyl-1-methylpyrrolidinium tetracyanoborate, and1-butyl-3-methylimidazolium trifluoromethanesulfonate.

In one embodiment, the AES is 1-butyl-3-methylimidazoliumtetrafluoroborate.

In one embodiment, the AES is 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide.

In one embodiment, the AES is 1-ethyl-3-methylimidazoliumtetrafluoroborate.

In one embodiment, the AES is 1-ethyl-3-methylimidazoliumtetracyanoborate.

In one embodiment, the AES is 1-hexyl-3-methylimidazoliumtetracyanoborate.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidiniumbis(trifluoromethylsulfonyl)imide.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidiniumtris(pentafluoroethyl)trifluorophosphate.

In one embodiment, the AES is 1-butyl-1-methylpyrrolidiniumtetracyanoborate.

In one embodiment, the AES is 1-butyl-3-methylimidazoliumtrifluoromethanesulfonate.

In another particular embodiment, one of the two R_(x) that are not H,is alkyl, e.g., methyl, and the other is an alkyl substituted with analkoxy. Moreover, it has been found that cations having an N,O-acetalskeleton structure of the formula (I) in the molecule have highelectrical conductivity, and that an ammonium cation included amongthese cations and having a pyrrolidine skeleton and an N,O-acetal groupis especially high in electrical conductivity and solubility in organicsolvents and supports relatively high voltage. As such, in oneembodiment, the advanced electrolyte system comprises a salt of thefollowing formula:

-   -   (1)        wherein R1 and R2 can be the same or different and are each        alkyl, and X— is an anion. In some embodiments, R₁ is        straight-chain or branched alkyl having 1 to 4 carbon atoms, R₂        is methyl or ethyl, and X⁻ is a cyanoborate-containing anion 11.        In a specific embodiment, X⁻ comprises [B(CN)]₄ and R₂ is one of        a methyl and an ethyl group. In another specific embodiment, R₁        and R₂ are both methyl. In addition, in one embodiment,        cyanoborate anions 11, X⁻ suited for the advanced electrolyte        system of the present invention include, [B(CN)4]⁻ or        [BFn(CN)4-n]⁻, where n=0, 1, 2 or 3.

Examples of cations of the AES of the present invention comprising aNovel Electrolyte Entity of formula (I), and which are composed of aquaternary ammonium cation shown in formula (I) and a cyanoborate anionare selected from N-methyl-N-methoxymethylpyrrolidinium(N-methoxymethyl-N-methylpyrrolidinium),N-ethyl-N-methoxymethylpyrrolidinium,N-methoxymethyl-N-n-propylpyrrolidinium,N-methoxymethyl-N-iso-propylpyrrolidinium,N-n-butyl-N-methoxymethylpyrrolidinium,N-iso-butyl-N-methoxymethylpyrrolidinium,N-tert-butyl-N-methoxymethylpyrrolidinium,N-ethoxymethyl-N-methylpyrrolidinium,N-ethyl-N-ethoxymethylpyrrolidinium(N-ethoxymethyl-N-ethylpyrrolidinium),N-ethoxymethyl-N-n-propylpyrrolidinium,N-ethoxymethyl-N-iso-propylpyrrolidinium,N-n-butyl-N-ethoxymethylpyrrolidinium,N-iso-butyl-N-ethoxymethylpyrrolidinium andN-tert-butyl-N-ethoxymethylpyrrolidinium. Other examples includeN-methyl-N-methoxymethylpyrrolidinium(N-methoxymethyl-N-methylpyrrolidinium),N-ethyl-N-methoxymethylpyrrolidinium andN-ethoxymethyl-N-methylpyrrolidinium.

Additional examples of the cation of formula (1) in combination withadditional anions may be selected fromN-methyl-N-methoxymethylpyrrolidinium tetracyanoborate(N-methoxymethyl-N-methylpyrrolidinium tetracyanoborate),N-ethyl-N-methoxymethylpyrrolidinium tetracyanoborate,N-ethoxymethyl-N-methylpyrrolidinium tetracyanoborate,N-methyl-N-methoxymethylpyrrolidinium bistrifluoromethanesulfonylimide,(N-methoxymethyl-N-methylpyrrolidiniumbistrifluoromethanesulfonylimide), N-ethyl-N-methoxymethylpyrrolidiniumbistrifluoromethanesulfonylimide, N-ethoxymethyl-N-methylpyrrolidiniumbistrifluoromethanesulfonylimide, N-methyl-N-methoxymethylpyrrolidiniumtrifluoromethanesulfolate(N-methoxymethyl-N-methyltrifluoromethanesulfolate).

When to be used as an electrolyte, the quaternary ammonium salt may beused as admixed with a suitable organic solvent. Useful solvents includecyclic carbonic acid esters, chain carbonic acid esters, phosphoric acidesters, cyclic ethers, chain ethers, lactone compounds, chain esters,nitrile compounds, amide compounds and sulfone compounds. Examples ofsuch compounds are given below although the solvents to be used are notlimited to these compounds.

Examples of cyclic carbonic acid esters are ethylene carbonate,propylene carbonate, butylene carbonate and the like, among whichpropylene carbonate is preferable.

Examples of chain carbonic acid esters are dimethyl carbonate,ethylmethyl carbonate, diethyl carbonate and the like, among whichdimethyl carbonate and ethylmethyl carbonate are preferred.

Examples of phosphoric acid esters are trimethyl phosphate, triethylphosphate, ethyldimethyl phosphate, diethylmethyl phosphate and thelike. Examples of cyclic ethers are tetrahydrofuran,2-methyltetrahydrofuran and the like. Examples of chain ethers aredimethoxyethane and the like. Examples of lactone compounds areã-butyrolactone and the like. Examples of chain esters are methylpropionate, methyl acetate, ethyl acetate, methyl formate and the like.Examples of nitrile compounds are acetonitrile and the like. Examples ofamide compounds are dimethylformamide and the like. Examples of sulfonecompounds are sulfolane, methyl sulfolane and the like. Cyclic carbonicacid esters, chain carbonic acid esters, nitrile compounds and sulfonecompounds may be particularly desirable, in some embodiments.

These solvents may be used singly, or at least two kinds of solvents maybe used in admixture. Examples of preferred organic solvent mixtures aremixtures of cyclic carbonic acid ester and chain carbonic acid estersuch as those of ethylene carbonate and dimethyl carbonate, ethylenecarbonate and ethylmethyl carbonate, ethylene carbonate and diethylcarbonate, propylene carbonate and dimethyl carbonate, propylenecarbonate and ethylmethyl carbonate and propylene carbonate and diethylcarbonate, mixtures of chain carbonic acid esters such as dimethylcarbonate and ethylmethyl carbonate, and mixtures of sulfolane compoundssuch as sulfolane and methylsulfolane. More preferable are mixtures ofethylene carbonate and ethylmethyl carbonate, propylene carbonate andethylmethyl carbonate, and dimethyl carbonate and ethylmethyl carbonate.

In some embodiments, when the quaternary ammonium salt of the inventionis to be used as an electrolyte, the electrolyte concentration is atleast 0.1 M, in some cases at least 0.5 M and may be at least 1 M. Ifthe concentration is less than 0.1 M, low electrical conductivity willresult, producing electrochemical devices of impaired performance. Theupper limit concentration is a separation concentration when theelectrolyte is a liquid salt at room temperature. When the solution doesnot separate, the limit concentration is 100%. When the salt is solid atroom temperature, the limit concentration is the concentration at whichthe solution is saturated with the salt.

In certain embodiments, the advanced electrolyte system (AES) may beadmixed with electrolytes other than those disclosed herein providedthat such combination does not significantly affect the advantagesachieved by utilization of the advanced electrolyte system, e.g., byaltering the performance or durability characteristics by greater than10%. Examples of electrolytes that may be suited to be admixed with theAES are alkali metal salts, quaternary ammonium salts, quaternaryphosphonium salts, etc. These electrolytes may be used singly, or atleast two kinds of them are usable in combination, as admixed with theAES disclosed herein. Useful alkali metal salts include lithium salts,sodium salts and potassium salts. Examples of such lithium salts arelithium hexafluorophosphate, lithium borofluoride, lithium perchlorate,lithium trifluoromethanesulfonate, sulfonylimide lithium,sulfonylmethide lithium and the like, which nevertheless are notlimitative. Examples of useful sodium salts are sodiumhexafluorophosphate, sodium borofluoride, sodium perchlorate, sodiumtrifluoromethanesulfonate, sulfonylimide sodium, sulfonylmethide sodiumand the like. Examples of useful potassium salts are potassiumhexafluorophosphate, potassium borofluoride, potassium perchlorate,potassium trifluoromethanesulfonate, sulfonylimide potassium,sulfonylmethide potassium and the like although these are notlimitative.

Useful quaternary ammonium salts that may be used in the combinationsdescribed above (i.e., which do not significantly affect the advantagesachieved by utilization of the advanced electrolyte system) includetetraalkylammonium salts, imidazolium salts, pyrazolium salts,pyridinium salts, triazolium salts, pyridazinium salts, etc., which arenot limitative. Examples of useful tetraalkylammonium salts aretetraethylammonium tetracyanoborate, tetramethylammoniumtetracyanoborate, tetrapropylammonium tetracyanoborate,tetrabutylammonium tetracyanoborate, triethylmethylammoniumtetracyanoborate, trimethylethylammonium tetracyanoborate,dimethyldiethylammonium tetracyanoborate, trimethylpropylammoniumtetracyanoborate, trimethylbutylammonium tetracyanoborate,dimethylethylpropylammonium tetracyanoborate,methylethylpropylbutylammonium tetracyanoborate,N,N-dimethylpyrrolidinium tetracyanoborate,N-ethyl-N-methylpyrrolidinium tetracyanoborate,N-methyl-N-propylpyrrolidinium tetracyanoborate,N-ethyl-N-propylpyrrolidinium tetracyanoborate, N,N-dimethylpiperidiniumtetracyanoborate, N-methyl-N-ethylpiperidinium tetracyanoborate,N-methyl-N-propylpiperidinium tetracyanoborate,N-ethyl-N-propylpiperidinium tetracyanoborate, N,N-dimethylmorpholiniumtetracyanoborate, N-methyl-N-ethylmorpholinium tetracyanoborate,N-methyl-N-propylmorpholinium tetracyanoborate,N-ethyl-N-propylmorpholinium tetracyanoborate and the like, whereasthese examples are not limitative.

Examples of imidazolium salts that may be used in the combinationsdescribed above (i.e., which do not significantly affect the advantagesachieved by utilization of the advanced electrolyte system) include1,3-dimethylimidazolium tetracyanoborate, 1-ethyl-3-methylimidazoliumtetracyanoborate, 1,3-diethylimidazolium tetracyanoborate,1,2-dimethyl-3-ethylimidazolium tetracyanoborate and1,2-dimethyl-3-propylimidazolium tetracyanoborate, but are not limitedto these. Examples of pyrazolium salts are 1,2-dimethylpyrazoliumtetracyanoborate, 1-methyl-2-ethylpyrazolium tetracyanoborate,1-propyl-2-methylpyrazolium tetracyanoborate and1-methyl-2-butylpyrazolium tetracyanoborate, but are not limited tothese. Examples of pyridinium salts are N-methylpyridiniumtetracyanoborate, N-ethylpyridinium tetracyanoborate, N-propylpyridiniumtetracyanoborate and N-butylpyridinium tetracyanoborate, but are notlimited to these. Examples of triazolium salts are 1-methyltriazoliumtetracyanoborate, 1-ethyltriazolium tetracyanoborate, 1-propyltriazoliumtetracyanoborate and 1-butyltriazolium tetracyanoborate, but are notlimited to these. Examples of pyridazinium salts are1-methylpyridazinium tetracyanoborate, 1-ethylpyridaziniumtetracyanoborate, 1-propylpyridazinium tetracyanoborate and1-butylpyridazinium tetracyanoborate, but are not limited to these.Examples of quaternary phosphonium salts are tetraethylphosphoniumtetracyanoborate, tetramethylphosphonium tetracyanoborate,tetrapropylphosphonium tetracyanoborate, tetrabutylphosphoniumtetracyanoborate, triethylmethylphosphonium tetrafluoroborate,trimethylethylphosphonium tetracyanoborate, dimethyldiethylphosphoniumtetracyanoborate, trimethylpropylphosphonium tetracyanoborate,trimethylbutylphosphonium tetracyanoborate,dimethylethylpropylphosphonium tetracyanoborate,methylethylpropylbutylphosphonium tetracyanoborate, but are not limitedto these.

In certain embodiments, the novel electrolytes selected herein for usethe advanced electrolyte systems may also be purified. Such purificationmay be performed using art-recognized techniques or the techniquesprovided herein. This purification may further improve thecharacteristics of the Novel Electrolyte Entities described herein.

Highly Purified Electrolytes

The advanced electrolyte systems of the present comprise, in oneembodiment, certain highly purified electrolytes for use in hightemperature ultracapacitors. In certain embodiments. The highly purifiedelectrolytes that comprise the AES of the present invention are thoseelectrolytes described below as well as those novel electrolytesdescribed above purified by the purification process described herein.The purification methods provided herein produce impurity levels thatafford an advanced electrolyte system with enhanced properties for usein high temperature applications, e.g., high temperatureultracapacitors, for example in a temperature range of about 80 degreesCelsius to about 210 degrees Celsius, e.g., about 80 degrees Celsius toabout 200 degrees Celsius, e.g., about 80 degrees Celsius to about 190degrees Celsius e.g., about 80 degrees Celsius to about 180 degreesCelsius e.g., about 80 degrees Celsius to about 170 degrees Celsiuse.g., about 80 degrees Celsius to about 160 degrees Celsius e.g., about80 degrees Celsius to about 150 degrees Celsius e.g., about 85 degreesCelsius to about 145 degrees Celsius e.g., about 90 degrees Celsius toabout 140 degrees Celsius e.g., about 95 degrees Celsius to about 135degrees Celsius e.g., about 100 degrees Celsius to about 130 degreesCelsius e.g., about 105 degrees Celsius to about 125 degrees Celsiuse.g., about 110 degrees Celsius to about 120 degrees Celsius.

Obtaining improved properties of the ultracapacitor 10 results in arequirement for better electrolyte systems than presently available. Forexample, it has been found that increasing the operational temperaturerange may be achieved by the significant reduction/removal of impuritiesfrom certain forms of known electrolytes. Impurities of particularconcern include water, halide ions (chloride, bromide, fluoride,iodide), free amines (ammonia), sulfate, and metal cations (Ag, Al, Ba,Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sr, Ti, Zn). Thehighly purified electrolyte product of such purification provideselectrolytes that are surprisingly far superior to the unpurifiedelectrolyte, and as such, fall with the advanced electrolyte systems ofthe present invention.

In a particular embodiment, the present invention provides a purifiedmixture of cation 9 and anion 11 and, in some instances a solvent, whichmay serve as the AES of the present invention which comprises less thanabout 5000 parts per million (ppm) of chloride ions; less than about1000 ppm of fluoride ions; and/or less than about 1000 ppm of water(e.g. less than about 2000 ppm of chloride ions; less than about lessthan about 200 ppm of fluoride ions; and/or less than about 200 ppm ofwater, e.g. less than about 1000 ppm of chloride ions; less than aboutless than about 100 ppm of fluoride ions; and/or less than about 100 ppmof water, e.g. less than about 500 ppm of chloride ions; less than aboutless than about 50 ppm of fluoride ions; and/or less than about 50 ppmof water, e.g. less than about 780 parts per million of chloride ions;less than about 11 parts per million of fluoride ions; and less thanabout 20 parts per million of water.)

Generally, impurities in the purified electrolyte are removed using themethods of purification described herein. For example, in someembodiments, a total concentration of halide ions (chloride, bromide,fluoride, iodide), may be reduced to below about 1,000 ppm. A totalconcentration of metallic species (e.g., Cd, Co, Cr, Cu, Fe, K, Li, Mo,Na, Ni, Pb, Zn, including an at least one of an alloy and an oxidethereof), may be reduced to below about 1,000 ppm. Further, impuritiesfrom solvents and precursors used in the synthesis process may bereduced to below about 1,000 ppm and can include, for example,bromoethane, chloroethane, 1-bromobutane, 1-chlorobutane,1-methylimidazole, ethyl acetate, methylene chloride and so forth.

In some embodiments, the impurity content of the ultracapacitor 10 hasbeen measured using ion selective electrodes and the Karl Fischertitration procedure, which has been applied to electrolyte 6 of theultracapacitor 10. In certain embodiments, it has been found that thetotal halide content in the ultracapacitor 10 according to the teachingsherein has been found to be less than about 200 ppm of halides (Cl⁻ andF⁻) and water content is less than about 100 ppm.

Impurities can be measured using a variety of techniques, such as, forexample, Atomic Absorption Spectrometry (AAS), Inductively CoupledPlasma-Mass Spectrometry (ICPMS), or simplified solubilizing andelectrochemical sensing of trace heavy metal oxide particulates. AAS isa spectro-analytical procedure for the qualitative and quantitativedetermination of chemical elements employing the absorption of opticalradiation (light) by free atoms in the gaseous state. The technique isused for determining the concentration of a particular element (theanalyte) in a sample to be analyzed. AAS can be used to determine overseventy different elements in solution or directly in solid samples.ICPMS is a type of mass spectrometry that is highly sensitive andcapable of the determination of a range of metals and several non-metalsat concentrations below one part in 10¹² (part per trillion). Thistechnique is based on coupling together an inductively coupled plasma asa method of producing ions (ionization) with a mass spectrometer as amethod of separating and detecting the ions. ICPMS is also capable ofmonitoring isotopic speciation for the ions of choice.

Additional techniques may be used for analysis of impurities. Some ofthese techniques are particularly advantageous for analyzing impuritiesin solid samples. Ion Chromatography (IC) may be used for determinationof trace levels of halide impurities in the electrolyte 6 (e.g., anionic liquid). One advantage of Ion Chromatography is that relevanthalide species can be measured in a single chromatographic analysis. ADionex AS9-HC column using an eluent consisting 20 mM NaOH and 10% (v/v)acetonitrile is one example of an apparatus that may be used for thequantification of halides from the ionic liquids. A further technique isthat of X-ray fluorescence.

X-ray fluorescence (XRF) instruments may be used to measure halogencontent in solid samples. In this technique, the sample to be analyzedis placed in a sample cup and the sample cup is then placed in theanalyzer where it is irradiated with X-rays of a specific wavelength.Any halogen atoms in the sample absorb a portion of the X-rays and thenreflect radiation at a wavelength that is characteristic for a givenhalogen. A detector in the instrument then quantifies the amount ofradiation coming back from the halogen atoms and measures the intensityof radiation. By knowing the surface area that is exposed, concentrationof halogens in the sample can be determined. A further technique forassessing impurities in a solid sample is that of pyrolysis.

Adsorption of impurities may be effectively measured through use ofpyrolysis and microcoulometers. Microcoulometers are capable of testingalmost any type of material for total chlorine content. As an example, asmall amount of sample (less than 10 milligrams) is either injected orplaced into a quartz combustion tube where the temperature ranges fromabout 600 degrees Celsius to about 1,000 degrees Celsius. Pure oxygen ispassed through the quartz tube and any chlorine containing componentsare combusted completely. The resulting combustion products are sweptinto a titration cell where the chloride ions are trapped in anelectrolyte solution. The electrolyte solution contains silver ions thatimmediately combine with any chloride ions and drop out of solution asinsoluble silver chloride. A silver electrode in the titration cellelectrically replaces the used up silver ions until the concentration ofsilver ions is back to where it was before the titration began. Bykeeping track of the amount of current needed to generate the requiredamount of silver, the instrument is capable of determining how muchchlorine was present in the original sample. Dividing the total amountof chlorine present by the weight of the sample gives the concentrationof chlorine that is actually in the sample. Other techniques forassessing impurities may be used.

Surface characterization and water content in the electrode 3 may beexamined, for example, by infrared spectroscopy techniques. The fourmajor absorption bands at around 1130, 1560, 3250 and 2300 cm⁻¹,correspond to íC═O in, íC═C in aryl, íO—H and íC—N, respectively. Bymeasuring the intensity and peak position, it is possible toquantitatively identify the surface impurities within the electrode 3.

Another technique for identifying impurities in the electrolyte 6 andthe ultracapacitor 10 is Raman spectroscopy. This spectroscopictechnique relies on inelastic scattering, or Raman scattering, ofmonochromatic light, usually from a laser in the visible, near infrared,or near ultraviolet range. The laser light interacts with molecularvibrations, phonons or other excitations in the system, resulting in theenergy of the laser photons being shifted up or down. Thus, thistechnique may be used to characterize atoms and molecules within theultracapacitor 10. A number of variations of Raman spectroscopy areused, and may prove useful in characterizing contents the ultracapacitor10.

Enhanced Electrolyte Combinations

The advanced electrolyte systems of the present comprise, in oneembodiment, include certain enhanced electrolyte combinations suitablefor use in temperature ranges from −40 degrees Celsius to 210 degreesCelsius, e.g., −40 degrees Celsius to 150 degrees Celsius, e.g., −30degrees Celsius to 150 degrees Celsius, e.g., −30 degrees Celsius to 140degrees Celsius, e.g., −20 degrees Celsius to 140 degrees Celsius, e.g.,−20 degrees Celsius to 130 degrees Celsius, e.g., −10 degrees Celsius to130 degrees Celsius, e.g., −10 degrees Celsius to 120 degrees Celsius,e.g., 0 degrees Celsius to 120 degrees Celsius, e.g., 0 degrees Celsiusto 110 degrees Celsius, e.g., 0 degrees Celsius to 100 degrees Celsius,e.g., 0 degrees Celsius to 90 degrees Celsius, e.g., 0 degrees Celsiusto 80 degrees Celsius, e.g., 0 degrees Celsius to 70 degrees Celsius,without a significant drop in performance or durability.

Generally, a higher degree of durability at a given temperature may becoincident with a higher degree of voltage stability at a lowertemperature. Accordingly, the development of a high temperaturedurability AES, with enhanced electrolyte combinations, generally leadsto simultaneous development of high voltage, but lower temperature AES,such that these enhanced electrolyte combinations described herein mayalso be useful at higher voltages, and thus higher energy densities, butat lower temperatures.

In one embodiment, the present invention provides an enhancedelectrolyte combination suitable for use in an energy storage cell,e.g., an ultracapacitor, comprising a novel mixture of electrolytesselected from the group consisting of an ionic liquid mixed with asecond ionic liquid, an ionic liquid mixed with an organic solvent, andan ionic liquid mixed with a second ionic liquid and an organic solvent:

wherein each ionic liquid is selected from the salt of any combinationof the following cations and anions, wherein the cations are selectedfrom the group consisting of 1-butyl-3-methylimidazolium,1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium,1-butyl-1-methylpiperidinium, butyltrimethylammonium,1-butyl-1-methylpyrrolidinium, trihexyltetradecylphosphonium, and1-butyl-3-methylimidaxolium; and the anions are selected from the groupconsisting of tetrafluoroborate, bis(trifluoromethylsulfonyl)imide,tetracyanoborate, and trifluoromethanesulfonate; and

wherein the organic solvent is selected from the group consisting oflinear sulfones (e.g., ethyl isopropyl sulfone, ethyl isobutyl sulfone,ethyl methyl sulfone, methyl isopropyl sulfone, isopropyl isobutylsulfone, isopropyl s-butyl sulfone, butyl isobutyl sulfone, and dimethylsulfone), linear carbonates (e.g., ethylene carbonate, propylenecarbonate, and dimethyl carbonate), and acetonitrile.

For example, given the combinations of cations and anions above, eachionic liquid may be selected from the group consisting of1-butyl-3-methylimidazolium tetrafluoroborate;1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide;1-ethyl-3-methylimidazolium tetrafluoroborate;1-ethyl-3-methylimidazolium tetracyanoborate;1-hexyl-3-methylimidazolium tetracyanoborate;1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide;1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate;1-butyl-1-methylpyrrolidinium tetracyanoborate;trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide,1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide,butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, and1-butyl-3-methylimidazolium trifluoromethanesulfonate.

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazoliumtetrafluoroborate.

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is 1-ethyl-3-methylimidazoliumtetrafluoroborate.

In certain embodiments, the ionic liquid is 1-ethyl-3-methylimidazoliumtetracyanoborate.

In certain embodiments, the ionic liquid is 1-hexyl-3-methylimidazoliumtetracyanoborate.

In certain embodiments, the ionic liquid is1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.

In one embodiment, the ionic liquid is 1-butyl-1-methylpyrrolidiniumtris(pentafluoroethyl)trifluorophosphate.

In certain embodiments, the ionic liquid is1-butyl-1-methylpyrrolidinium tetracyanoborate.

In certain embodiments, the ionic liquid istrihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is 1-butyl-1-methylpiperidiniumbis(trifluoromethylsulfonyl)imide.

In certain embodiments, the ionic liquid is butyltrimethylammoniumbis(trifluoromethylsulfonyl)imide

In certain embodiments, the ionic liquid is 1-butyl-3-methylimidazoliumtrifluoromethanesulfonate.

In certain embodiments, the organic solvent is selected from ethylisopropyl sulfone, ethyl isobutyl sulfone, ethyl methyl sulfone, methylisopropyl sulfone, isopropyl isobutyl sulfone, isopropyl s-butylsulfone, butyl isobutyl sulfone, or bimethyl sulfone, linear sulfones.

In certain embodiments, the organic solvent is selected frompolypropylene carbonate, propylene carbonate, dimethyl carbonate,ethylene carbonate.

In certain embodiments, the organic solvent is acetonitrile.

In certain embodiments, the enhanced electrolyte composition is an ionicliquid with an organic solvent, wherein the organic solvent is 55%-90%,e.g., 37.5%, by volume of the composition.

In certain embodiments, the enhanced electrolyte composition is an ionicliquid with a second ionic liquid, wherein one ionic liquid is 5%-90%,e.g., 60%, by volume of the composition.

The enhanced electrolyte combinations of the present invention provide awider temperature range performance for an individual capacitor (e.g.without a significant drop in capacitance and/or increase in ESR whentransitioning between two temperatures, e.g. without more than a 90%decrease in capacitance and/or a 1000% increase in ESR whentransitioning from about +30° C. to about −40° C.), and increasedtemperature durability for an individual capacitor (e.g., less than a50% decrease in capacitance at a given temperature after a given timeand/or less than a 100% increase in ESR at a given temperature after agiven time, and/or less than 10 A/L of leakage current at a giventemperature after a given time, e.g., less than a 40% decrease incapacitance and/or a 75% increase in ESR, and/or less than 5 A/L ofleakage current, e.g., less than a 30% decrease in capacitance and/or a50% increase in ESR, and/or less than 1 A/L of leakage current).

Without wishing to be bound by theory, the combinations described aboveprovide enhanced eutectic properties that affect the freezing point ofthe advanced electrolyte system to afford ultracapacitors that operatewithin performance and durability standards at temperatures of down to−40 degrees Celsius.

As described above for the novel electrolytes of the present invention,in certain embodiments, the advanced electrolyte system (AES) may beadmixed with electrolytes provided that such combination does notsignificantly affect the advantages achieved by utilization of theadvanced electrolyte system.

In certain embodiments, the enhanced electrolyte combinations areselected herein for use the advanced electrolyte systems may also bepurified. Such purification may be performed using art-recognizedtechniques or techniques provided herein.

B. Electrodes

The EDLC includes at least one pair of electrode 3 (where the electrode3 may be referred to as a negative electrodes 33 and a positiveelectrodes 34, merely for purposes of referencing herein). Whenassembled into the ultracapacitor 10, each of the electrode 3 presents adouble layer of charge at an electrolyte interface. In some embodiments,a plurality of electrode 3 is included (for example, in someembodiments, at least two pairs of electrode 3 are included). However,for purposes of discussion, only one pair of electrode 3 are shown. As amatter of convention herein, at least one of the electrodes 33/34 uses acarbon-based energy storage media 1 (as discussed further herein) toprovide energy storage. However, for purposes of discussion herein, itis generally assumed that each of the electrodes includes thecarbon-based energy storage media 1.

i. Current Collector

Current Collector

Each of the electrode 3 includes a respective current collector 2 (alsoreferred to as a “charge collector”). In some embodiments, the electrode3 are separated by a separator 5. In general, the separator 5 is a thinstructural material (usually a sheet) used to separate the negativeelectrode 3 from the positive electrode 3. The separator 5 may alsoserve to separate pairs of the electrode 3. Note that, in someembodiments, the carbon-based energy storage media 1 may not be includedon one or both of the electrode 3. That is, in some embodiments, arespective electrode 3 might consist of only the current collector 2.The material used to provide the current collector 2 could be roughened,anodized or the like to increase a surface area thereof. In theseembodiments, the current collector 2 alone may serve as the electrode 3.With this in mind, however, as used herein, the term “electrode 3”generally refers to a combination of the energy storage media 1 and thecurrent collector 2 (but this is not limiting, for at least theforegoing reason).

Energy Storage Media

In the exemplary ultracapacitor 10, the energy storage media 1 is formedof carbon nanotubes. The energy storage media 1 may include othercarbonaceous materials including, for example, activated carbon, carbonfibers, rayon, graphene, aerogel, carbon cloth, and a plurality of formsof carbon nanotubes. Activated carbon electrodes can be manufactured,for example, by producing a carbon base material by carrying out a firstactivation treatment to a carbon material obtained by carbonization of acarbon compound, producing a formed body by adding a binder to thecarbon base material, carbonizing the formed body, and finally producingan active carbon electrode by carrying out a second activation treatmentto the carbonized formed body. Carbon fiber electrodes can be produced,for example, by using paper or cloth pre-form with high surface areacarbon fibers.

In an exemplary method for fabricating carbon nanotubes, an apparatusfor producing an aligned carbon-nanotube aggregate includes apparatusfor synthesizing the aligned carbon-nanotube aggregate on a basematerial having a catalyst on a surface thereof. The apparatus includesa formation unit that processes a formation step of causing anenvironment surrounding the catalyst to be an environment of a reducinggas and heating at least either the catalyst or the reducing gas; agrowth unit that processes a growth step of synthesizing the alignedcarbon-nanotube aggregate by causing the environment surrounding thecatalyst to be an environment of a raw material gas and by heating atleast either the catalyst or the raw material gas; and a transfer unitthat transfers the base material at least from the formation unit to thegrowth unit. A variety of other methods and apparatus may be employed toprovide the aligned carbon-nanotube aggregate.

In some embodiments, material used to form the energy storage media 1may include material other than pure carbon (and the various forms ofcarbon as may presently exist or be later devised). That is, variousformulations of other materials may be included in the energy storagemedia 1. More specifically, and as a non-limiting example, at least onebinder material may be used in the energy storage media 1, however, thisis not to suggest or require addition of other materials (such as thebinder material). In general, however, the energy storage media 1 issubstantially formed of carbon, and may therefore referred to herein asa “carbonaceous material,” as a “carbonaceous layer” and by othersimilar terms. In short, although formed predominantly of carbon, theenergy storage media 1 may include any form of carbon (as well as anyadditives or impurities as deemed appropriate or acceptable) to providefor desired functionality as energy storage media 1.

In one set of embodiments, the carbonaceous material includes at leastabout 60% elemental carbon by mass, and in other embodiments at leastabout 75%, 85%, 90%, 95% or 98% by mass elemental carbon.

Carbonaceous material can include carbon in a variety forms, includingcarbon black, graphite, and others. The carbonaceous material caninclude carbon particles, including nanoparticles, such as nanotubes,nanorods, graphene sheets in sheet form, and/or formed into cones, rods,spheres (buckyballs) and the like.

Some embodiments of various forms of carbonaceous material suited foruse in energy storage media 1 are provided herein as examples. Theseembodiments provide robust energy storage and are well suited for use inthe electrode 3. It should be noted that these examples are illustrativeand are not limiting of embodiments of carbonaceous material suited foruse in energy storage media 1.

In certain embodiments, the porosity of the energy storage media 1 ofeach electrode may be selected based on the size of the respectiveelectrolyte to improve the performance of the capacitor.

An exemplary process for complimenting the energy storage media 1 withthe current collector 2 to provide the electrode 3 is now provided.Referring now to FIG. 2, a substrate 14 that is host to carbonaceousmaterial in the form of carbon nanotube aggregate (CNT) is shown. In theembodiment shown, the substrate 14 includes a base material 17 with athin layer of a catalyst 18 disposed thereon.

In general, the substrate 14 is at least somewhat flexible (i.e., thesubstrate 14 is not brittle), and is fabricated from components that canwithstand environments for deposition of the energy storage media 1(e.g., CNT). For example, the substrate 14 may withstand ahigh-temperature environment of between about 400 degrees Celsius toabout 1,100 degrees Celsius. A variety of materials may be used for thesubstrate 14, as determined appropriate.

Once the energy storage media 1 (e.g., CNT) has been fabricated on thesubstrate 14, the current collector 2 may be disposed thereon. In someembodiments, the current collector 2 is between about 0.5 micrometers(μm) to about 25 micrometers (μm) thick. In some embodiments, thecurrent collector 2 is between about 20 micrometers (μm) to about 40micrometers (μm) thick. The current collector 2 may appear as a thinlayer, such as layer that is applied by chemical vapor deposition (CVD),sputtering, e-beam, thermal evaporation or through another suitabletechnique. Generally, the current collector 2 is selected for itsproperties such as conductivity, being electrochemically inert andcompatible with the energy storage media 1 (e.g., CNT). Some exemplarymaterials include aluminum, platinum, gold, tantalum, titanium, and mayinclude other materials as well as various alloys.

Once the current collector 2 is disposed onto the energy storage media 1(e.g., CNT), an electrode element 15 is realized. Each electrode element15 may be used individually as the electrode 3, or may be coupled to atleast another electrode element 15 to provide for the electrode 3.

Once the current collector 2 has been fabricated according to a desiredstandard, post-fabrication treatment may be undertaken. Exemplarypost-treatment includes heating and cooling of the energy storage media1 (e.g., CNT) in a slightly oxidizing environment. Subsequent tofabrication (and optional post-treatment), a transfer tool may beapplied to the current collector 2.

In one embodiment of an application of transfer tool 13 to the currentcollector 2, the transfer tool 13 is a thermal release tape, used in a“dry” transfer method. Exemplary thermal release tape is manufactured byNITTO DENKO CORPORATION of Fremont, Calif. and Osaka, Japan. Onesuitable transfer tape is marketed as REVALPHA. This release tape may becharacterized as an adhesive tape that adheres tightly at roomtemperature and can be peeled off by heating. This tape, and othersuitable embodiments of thermal release tape, will release at apredetermined temperature. Advantageously, the release tape does notleave a chemically active residue on the electrode element 15.

In another process, referred to as a “wet” transfer method, tapedesigned for chemical release may be used. Once applied, the tape isthen removed by immersion in a solvent. The solvent is designed todissolve the adhesive.

In other embodiments, the transfer tool 13 uses a “pneumatic” method,such as by application of suction to the current collector 2. Thesuction may be applied, for example, through a slightly oversized paddlehaving a plurality of perforations for distributing the suction. Inanother example, the suction is applied through a roller having aplurality of perforations for distributing the suction. Suction drivenembodiments offer advantages of being electrically controlled andeconomic as consumable materials are not used as a part of the transferprocess. Other embodiments of the transfer tool 13 may be used.

Once the transfer tool 13 has been temporarily coupled to the currentcollector 2, the electrode element 15 is gently removed from thesubstrate 14. The removal generally involves peeling the energy storagemedia 1 (e.g., CNT) from the substrate 14, beginning at one edge of thesubstrate 14 and energy storage media 1 (e.g., CNT).

Subsequently, the transfer tool 13 may be separated from the electrodeelement 15. In some embodiments, the transfer tool 13 is used to installthe electrode element 15. For example, the transfer tool 13 may be usedto place the electrode element 15 onto the separator 5. In general, onceremoved from the substrate 14, the electrode element 15 is available foruse.

In instances where a large electrode 3 is desired, a plurality of theelectrode elements 15 may be mated. A plurality of the electrodeelements 15 may be mated by, for example, coupling a coupling 52 to eachelectrode element 15 of the plurality of electrode elements 15. Themated electrode elements 15 provide for an embodiment of the electrode3.

In some embodiments, the coupling 22 is coupled to each of the electrodeelements 15 at a weld 21. Each of the welds 21 may be provided as anultrasonic weld 21. It has been found that ultrasonic welding techniquesare particularly well suited to providing each weld 21. That is, ingeneral, the aggregate of energy storage media 1 (e.g., CNT) is notcompatible with welding, where only a nominal current collector, such asdisclosed herein is employed. As a result, many techniques for joiningelectrode elements 15 are disruptive, and damage the element 15.However, in other embodiments, other forms of coupling are used, and thecoupling 22 is not a weld 21.

The coupling 22 may be a foil, a mesh, a plurality of wires or in otherforms. Generally, the coupling 22 is selected for properties such asconductivity and being electrochemically inert. In some embodiments, thecoupling 22 is fabricated from the same material(s) as are present inthe current collector 2.

In some embodiments, the coupling 22 is prepared by removing an oxidelayer thereon. The oxide may be removed by, for example, etching thecoupling 22 before providing the weld 21. The etching may beaccomplished, for example, with potassium hydroxide (KOH). The electrode3 may be used in a variety of embodiments of the ultracapacitor 10. Forexample, the electrode 3 may be rolled up into a “jelly roll” type ofenergy storage.

Separator

The separator 5 may be fabricated from various materials. In someembodiments, the separator 5 is non-woven glass. The separator 5 mayalso be fabricated from fiberglass, ceramics and fluoro-polymers, suchas polytetrafluoroethylene (PTFE), commonly marketed as TEFLON™ byDuPont Chemicals of Wilmington, Del. For example, using non-woven glass,the separator 5 can include main fibers and binder fibers each having afiber diameter smaller than that of each of the main fibers and allowingthe main fibers to be bonded together.

For longevity of the ultracapacitor 10 and to assure performance at hightemperature, the separator 5 should have a reduced amount of impuritiesand in particular, a very limited amount of moisture contained therein.In particular, it has been found that a limitation of about 200 ppm ofmoisture is desired to reduce chemical reactions and improve thelifetime of the ultracapacitor 10, and to provide for good performancein high temperature applications. Some embodiments of materials for usein the separator 5 include polyamide, polytetrafluoroethylene (PTFE),polyetheretherketone (PEEK), aluminum oxide (Al₂O₃), fiberglass, andglass-reinforced plastic (GRP).

In general, materials used for the separator 5 are chosen according tomoisture content, porosity, melting point, impurity content, resultingelectrical performance, thickness, cost, availability and the like. Insome embodiments, the separator 5 is formed of hydrophobic materials.

Accordingly, procedures may be employed to ensure excess moisture iseliminated from each separator 5. Among other techniques, a vacuumdrying procedure may be used. A selection of materials for use in theseparator 5 is provided in Table 7. Some related performance data isprovided in Table 8.

TABLE 7 Separator Materials Melting PPM H₂O PPM H₂O Vacuum dry Materialpoint unbaked baked procedure Polyamide 256° C. 2052  20 180° C. for 24h Polytetrafluoroethylene, 327° C.  286 135 150° C. for 24 h PTFEPolyether ether ketone, 256° C.  130  50 215° C. for 12 h PEEK AluminumOxide, 330° C. 1600 100 215° C. for 24 h Al₂O₃ Fiberglass (GRP) 320° C.2000 167 215° C. for 12 h

TABLE 8 Separator Performance Data ESR 1^(st) ESR 2^(nd) After 10Material μm Porosity test (Ω) test (Ω) CV Polyamide  42 Nonwoven 1.0691.069 1.213 PEEK  45 Mesh 1.665 1.675 2.160 PEEK 60%  25 60% 0.829 0.8400.883 Fiberglass (GRP) 160 Nonwoven 0.828 0.828 0.824 Aluminum  25 —2.400 2.400 2.400 Oxide, Al₂O₃

In order to collect data for Table 7, two electrode 3, based oncarbonaceous material, were provided. The electrode 3 were disposedopposite to and facing each other. Each of the separators 5 were placedbetween the electrode 3 to prevent a short circuit. The three componentswere then wetted with electrolyte 6 and compressed together. Twoaluminum bars and PTFE material was used as an external structure toenclose the resulting ultracapacitor 10.

The ESR 1^(st) test and ESR 2^(nd) test were performed with the sameconfiguration one after the other. The second test was run five minutesafter the first test, leaving time for the electrolyte 6 to further soakinto the components.

In certain embodiments, the ultracapacitor 10 does not include theseparator 5. For example, in particular embodiments, such as where theelectrode 3 are assured of physical separation by a geometry ofconstruction, it suffices to have electrolyte 6 alone between theelectrode 3. More specifically, and as an example of physicalseparation, one such ultracapacitor 10 may include electrode 3 that aredisposed within a housing such that separation is assured on acontinuous basis. A bench-top example would include an ultracapacitor 10provided in a beaker.

Storage Cell

Once assembled, the electrode 3 and the separator 5 provide a storagecell 12. Generally, the storage cell 12 is formed into one of a woundform or prismatic form which is then packaged into a cylindrical orprismatic housing 7. Once the electrolyte 6 has been included, thehousing 7 may be hermetically sealed. In various examples, the packageis hermetically sealed by techniques making use of laser, ultrasonic,and/or welding technologies. In addition to providing robust physicalprotection of the storage cell 12, the housing 7 is configured withexternal contacts to provide electrical communication with respectiveterminals 8 within the housing 7. Each of the terminals 8, in turn,provides electrical access to energy stored in the energy storage media1, generally through electrical leads which are coupled to the energystorage media 1.

Generally, the ultracapacitor 10 disclosed herein is capable ofproviding a hermetic seal that has a leak rate no greater than about5.0×10⁻⁶ atm-cc/sec, and may exhibit a leak rate no higher than about5.0×10⁻¹⁰ atm-cc/sec. It is also considered that performance of asuccessfully hermetic seal is to be judged by the user, designer ormanufacturer as appropriate, and that “hermetic” ultimately implies astandard that is to be defined by a user, designer, manufacturer orother interested party.

Leak detection may be accomplished, for example, by use of a tracer gas.Using tracer gas such as helium for leak testing is advantageous as itis a dry, fast, accurate and non destructive method. In one example ofthis technique, the ultracapacitor 10 is placed into an environment ofhelium. The ultracapacitor 10 is subjected to pressurized helium. Theultracapacitor 10 is then placed into a vacuum chamber that is connectedto a detector capable of monitoring helium presence (such as an atomicabsorption unit). With knowledge of pressurization time, pressure andinternal volume, the leak rate of the ultracapacitor 10 may bedetermined.

In some embodiments, at least one lead (which may also be referred toherein as a “tab”) is electrically coupled to a respective one of thecurrent collectors 2. A plurality of the leads (accordingly to apolarity of the ultracapacitor 10) may be grouped together and coupledto into a respective terminal 8. In turn, the terminal 8 may be coupledto an electrical access, referred to as a “contact” (e.g., one of thehousing 7 and an external electrode (also referred to herein forconvention as a “feed-through” or “pin”)).

Housing of Capacitor

FIG. 5 depicts aspects of an exemplary housing 7. Among other things,the housing 7 provides structure and physical protection for theultracapacitor 10. In this example, the housing 7 includes an annularcylindrically shaped body 10 and a complimentary cap 24. In thisembodiment, the cap 24 includes a central portion that has been removedand filled with an electrical insulator 26. A cap feed-through 19penetrates through the electrical insulator 26 to provide users withaccess to the stored energy. Moreover, the housing may also include aninner barrier 30.

Although this example depicts only one feed-through 19 on the cap 24, itshould be recognized that the construction of the housing 7 is notlimited by the embodiments discussed herein. For example, the cap 24 mayinclude a plurality of feed-throughs 19. In some embodiments, the body10 includes a second, similar cap 24 at the opposing end of the annularcylinder. Further, it should be recognized that the housing 7 is notlimited to embodiments having an annular cylindrically shaped body 10.For example, the housing 7 may be a clamshell design, a prismaticdesign, a pouch, or of any other design that is appropriate for theneeds of the designer, manufacturer or user.

Referring now to FIG. 6, there is shown an exemplary energy storage cell12. In this example, the energy storage cell 12 is a “jelly roll” typeof energy storage. In these embodiments, the energy storage materialsare rolled up into a tight package. A plurality of leads generally formeach terminal 8 and provide electrical access to the appropriate layerof the energy storage cell 12. Generally, when assembled, each terminal8 is electrically coupled to the housing 7 (such as to a respectivefeed-through 19 and/or directly to the housing 7). The energy storagecell 12 may assume a variety of forms. There are generally at least twoplurality of leads (e.g., terminals 8), one for each current collector2.

A highly efficient seal of the housing 7 is desired. That is, preventingintrusion of the external environment (such as air, humidity, etc,)helps to maintain purity of the components of the energy storage cell12. Further, this prevents leakage of electrolyte 6 from the energystorage cell 12.

In this example, the cap 24 is fabricated with an outer diameter that isdesigned for fitting snugly within an inner diameter of the body 10.When assembled, the cap 24 may be welded into the body 10, thusproviding users with a hermetic seal. Exemplary welding techniquesinclude laser welding and TIG welding, and may include other forms ofwelding as deemed appropriate.

Common materials for the housing 7 include stainless steel, aluminum,tantalum, titanium, nickel, copper, tin, various alloys, laminates, andthe like. Structural materials, such as some polymer-based materials maybe used in the housing 7 (generally in combination with at least somemetallic components).

In some embodiments, a material used for construction of the body 10includes aluminum, which may include any type of aluminum or aluminumalloy deemed appropriate by a designer or fabricator (all of which arebroadly referred to herein simply as “aluminum”). Various alloys,laminates, and the like may be disposed over (e.g., clad to) thealuminum (the aluminum being exposed to an interior of the body 10).Additional materials (such as structural materials or electricallyinsulative materials, such as some polymer-based materials) may be usedto compliment the body and/or the housing 7. The materials disposed overthe aluminum may likewise be chosen by what is deemed appropriate by adesigner or fabricator.

In some embodiments, the multi-layer material is used for internalcomponents. For example, aluminum may be clad with stainless steel toprovide for a multi-layer material in at least one of the terminals 8.In some of these embodiments, a portion of the aluminum may be removedto expose the stainless steel. The exposed stainless steel may then beused to attach the terminal 8 to the feed-through 19 by use of simplewelding procedures.

Using the clad material for internal components may call for particularembodiments of the clad material. For example, it may be beneficial touse clad material that include aluminum (bottom layer), stainless steeland/or tantalum (intermediate layer) and aluminum (top layer), whichthus limits exposure of stainless steel to the internal environment ofthe ultracapacitor 10. These embodiments may be augmented by, forexample, additional coating with polymeric materials, such as PTFE.

Accordingly, providing a housing 7 that takes advantage of multi-layeredmaterial provides for an energy storage that exhibits leakage currentwith comparatively low initial values and substantially slower increasesin leakage current over time in view of the prior art. Significantly,the leakage current of the energy storage remains at practical (i.e.,desirably low) levels when the ultracapacitor 10 is exposed to ambienttemperatures for which prior art capacitors would exhibit prohibitivelylarge initial values of leakage current and/or prohibitively rapidincreases in leakage current over time.

Additionally, the ultracapacitor 10 may exhibit other benefits as aresult of reduced reaction between the housing 7 and the energy storagecell 12. For example, an effective series resistance (ESR) of the energystorage may exhibit comparatively lower values over time. Further, theunwanted chemical reactions that take place in a prior art capacitoroften create unwanted effects such as out-gassing, or in the case of ahermetically sealed housing, bulging of the housing 7. In both cases,this leads to a compromise of the structural integrity of the housing 7and/or hermetic seal of the energy storage. Ultimately, this may lead toleaks or catastrophic failure of the prior art capacitor. These effectsmay be substantially reduced or eliminated by the application of adisclosed barrier.

By use of a multi-layer material (e.g., a clad material), stainlesssteel may be incorporated into the housing 7, and thus components withglass-to-metal seals may be used. The components may be welded to thestainless steel side of the clad material using techniques such as laseror resistance welding, while the aluminum side of the clad material maybe welded to other aluminum parts (e.g., the body 10).

In some embodiments, an insulative polymer may be used to coat parts ofthe housing 7. In this manner, it is possible to insure that thecomponents of the energy storage are only exposed to acceptable types ofmetal (such as the aluminum). Exemplary insulative polymer includes PFA,FEP, TFE, and PTFE. Suitable polymers (or other materials) are limitedonly by the needs of a system designer or fabricator and the propertiesof the respective materials. Reference may be had to FIG. 17, where asmall amount of insulative material 39 is included to limit exposure ofelectrolyte 6 to the stainless steel of the sleeve 51 and thefeed-through 19. In this example, the terminal 8 is coupled to thefeed-through 19, such as by welding, and then coated with the insulativematerial 39.

Housing Cap

Although this example depicts only one feed-through 19 on the cap 24, itshould be recognized that the construction of the housing 7 is notlimited by the embodiments discussed herein. For example, the cap 24 mayinclude a plurality of feed-throughs 19. In some embodiments, the body10 includes a second, similar cap 24 at an opposing end of the annularcylinder. Further, it should be recognized that the housing 7 is notlimited to embodiments having an annular cylindrically shaped body 10.For example, the housing 7 may be a clamshell design, a prismaticdesign, a pouch, or of any other design that is appropriate for theneeds of the designer, manufacturer or user.

Referring now to FIG. 12, aspects of embodiments of a blank 34 for thecap 24 are shown. In FIG. 12A, the blank 34 includes a multi-layermaterial. A layer of a first material 41 may be aluminum. A layer of asecond material 42 may be stainless steel. In the embodiments of FIG.12, the stainless steel is clad onto the aluminum, thus providing for amaterial that exhibits a desired combination of metallurgicalproperties. That is, in the embodiments provided herein, the aluminum isexposed to an interior of the energy storage cell (i.e., the housing),while the stainless steel is exposed to exterior. In this manner,advantageous electrical properties of the aluminum are enjoyed, whilestructural properties (and metallurgical properties, i.e., weldability)of the stainless steel are relied upon for construction. The multi-layermaterial may include additional layers as deemed appropriate.

As mentioned above, the layer of first material 41 is clad onto (orwith) the layer of second material 42. Referring still to FIG. 12A, inone embodiment, a sheet of flat stock (as shown) is used to provide theblank 34 to create a flat cap 24. A portion of the layer of secondmaterial 42 may be removed (such as around a circumference of the cap24) in order to facilitate attachment of the cap 24 to the body 10. InFIG. 12B, another embodiment of the blank 34 is shown. In this example,the blank 34 is provided as a sheet of clad material that is formed intoa concave configuration. In FIG. 12C, the blank 34 is provided as asheet of clad material that is formed into a convex configuration. Thecap 24 that is fabricated from the various embodiments of the blank 34(such as those shown in FIG. 12), are configured to support welding tothe body 10 of the housing 7. More specifically, the embodiment of FIG.12B is adapted for fitting within an inner diameter of the body 10,while the embodiment of FIG. 12C is adapted for fitting over an outerdiameter of the body 10. In various alternative embodiments, the layersof clad material within the sheet may be reversed.

Referring now to FIG. 13, there is shown an embodiment of an electrodeassembly 50. The electrode assembly 50 is designed to be installed intothe blank 34 and to provide electrical communication from the energystorage media to a user. Generally, the electrode assembly 50 includes asleeve 51. The sleeve 51 surrounds the insulator 26, which in turnsurrounds the feed-through 19. In this example, the sleeve 51 is anannular cylinder with a flanged top portion.

In order to assemble the cap 24, a perforation (not shown) is made inthe blank 34. The perforation has a geometry that is sized to match theelectrode assembly 50. Accordingly, the electrode assembly 50 isinserted into perforation of the blank 34. Once the electrode assembly50 is inserted, the electrode assembly 50 may be affixed to the blank 34through a technique such as welding. The welding may be laser weldingwhich welds about a circumference of the flange of sleeve 51. Referringto FIG. 14, points 61 where welding is performed are shown. In thisembodiment, the points 61 provide suitable locations for welding ofstainless steel to stainless steel, a relatively simple weldingprocedure. Accordingly, the teachings herein provide for welding theelectrode assembly 50 securely into place on the blank 34.

Material for constructing the sleeve 51 may include various types ofmetals or metal alloys. Generally, materials for the sleeve 51 areselected according to, for example, structural integrity and bondability(to the blank 34). Exemplary materials for the sleeve 51 include 304stainless steel or 316 stainless steel. Material for constructing thefeed-through 19 may include various types of metals or metal alloys.Generally, materials for the feed-through 19 are selected according to,for example, structural integrity and electrical conductance. Exemplarymaterials for the electrode include 446 stainless steel or 52 alloy.

Generally, the insulator 26 is bonded to the sleeve 51 and thefeed-through 19 through known techniques (i.e., glass-to-metal bonding).Material for constructing the insulator 26 may include, withoutlimitation, various types of glass, including high temperature glass,ceramic glass or ceramic materials. Generally, materials for theinsulator are selected according to, for example, structural integrityand electrical resistance (i.e., electrical insulation properties).

Use of components (such as the foregoing embodiment of the electrodeassembly 50) that rely on glass-to-metal bonding as well as use ofvarious welding techniques provides for hermetic sealing of the energystorage. Other components may be used to provide hermetic sealing aswell. As used herein, the term “hermetic seal” generally refers to aseal that exhibits a leak rate no greater than that which is definedherein. However, it is considered that the actual seal efficacy mayperform better than this standard.

Additional or other techniques for coupling the electrode assembly 50 tothe blank 34 include use of a bonding agent under the flange of thesleeve 51 (between the flange and the layer of second material 42), whensuch techniques are considered appropriate.

Referring now to FIG. 15, the energy storage cell 12 is disposed withinthe body 10. The at least one terminal 8 is coupled appropriately (suchas to the feed-through 19), and the cap 24 is mated with the body 10 toprovide for the ultracapacitor 10.

Once assembled, the cap 24 and the body 10 may be sealed. FIG. 22depicts various embodiments of the assembled energy storage (in thiscase, the ultracapacitor 10). In FIG. 16A, a flat blank 34 (see FIG.12A) is used to create a flat cap 24. Once the cap 24 is set on the body10, the cap 24 and the body 10 are welded to create a seal 62. In thiscase, as the body 10 is an annular cylinder, the weld proceedscircumferentially about the body 10 and cap 24 to provide the seal 62.In a second embodiment, shown in FIG. 16B, the concave blank 34 (seeFIG. 12B) is used to create a concave cap 24. Once the cap 24 is set onthe body 10, the cap 24 and the body 10 are welded to create the seal62. In a third embodiment, shown in FIG. 16C, the convex blank 34 (seeFIG. 12C) is used to create a convex cap 24. Once the cap 24 is set onthe body 10, the cap 24 and the body 10 may be welded to create the seal62.

As appropriate, clad material may be removed (by techniques such as, forexample, machining or etching, etc,) to expose other metal in themulti-layer material. Accordingly, in some embodiments, the seal 62 mayinclude an aluminum-to-aluminum weld. The aluminum-to-aluminum weld maybe supplemented with other fasteners, as appropriate.

Other techniques may be used to seal the housing 7. For example, laserwelding, TIG welding, resistance welding, ultrasonic welding, and otherforms of mechanical sealing may be used. It should be noted, however,that in general, traditional forms of mechanical sealing alone are notadequate for providing the robust hermetic seal offered in theultracapacitor 10.

Refer now to FIG. 12 in which aspects of assembly another embodiment ofthe cap 24 are depicted. FIG. 12A depicts a template (i.e., the blank34) that is used to provide a body of the cap 24. The template isgenerally sized to mate with the housing 7 of an appropriate type ofenergy storage cell (such as the ultracapacitor 10). The cap 24 may beformed by initially providing the template forming the template,including a dome 37 within the template (shown in FIG. 12B) and by thenperforating the dome 37 to provide a through-way 32 (shown in FIG. 12C).Of course, the blank 34 (e.g., a circular piece of stock) may be pressedor otherwise fabricated such that the foregoing features aresimultaneously provided.

In general, and with regard to these embodiments, the cap may be formedof aluminum, or an alloy thereof. However, the cap may be formed of anymaterial that is deemed suitable by a manufacturer, user, designer andthe like. For example, the cap 24 may be fabricated from steel andpassivated (i.e., coated with an inert coating) or otherwise preparedfor use in the housing 7.

Referring now also to FIG. 19, there is shown another embodiment of theelectrode assembly 50. In these embodiments, the electrode assembly 50includes the feed-through 19 and a hemispherically shaped materialdisposed about the feed-through 19. The hemispherically shaped materialserves as the insulator 26, and is generally shaped to conform to thedome 37. The hemispheric insulator 26 may be fabricated of any suitablematerial for providing a hermetic seal while withstanding the chemicalinfluence of the electrolyte 6. Exemplary materials include PFA(perfluoroalkoxy polymer), FEP (fluorinated ethylene-propylene), PVF(polyvinylfluoride), TFE (tetrafluoroethylene), CTFE(chlorotrifluoroethylene), PCTFE (polychlorotrifluoroethylene), ETFE(polyethylenetetrafluoroethylene), ECTFE(polyethylenechlorotrifluoroethylene), PTFE (polytetrafluoroethylene),another fluoropolymer based material as well as any other material thatmay exhibit similar properties (in varying degrees) and provide forsatisfactory performance (such as by exhibiting, among other things, ahigh resistance to solvents, acids, and bases at high temperatures, lowcost and the like).

The feed-through 19 may be formed of aluminum, or an alloy thereof.However, the feed-through 19 may be formed of any material that isdeemed suitable by a manufacturer, user, designer and the like. Forexample, the feed-through 19 may be fabricated from steel and passivated(i.e., coated with an inert coating, such as silicon) or otherwiseprepared for use in the electrode assembly 50. An exemplary techniquefor passivation includes depositing a coating of hydrogenated amorphoussilicon on the surface of the substrate and functionalizing the coatedsubstrate by exposing the substrate to a binding reagent having at leastone unsaturated hydrocarbon group under pressure and elevatedtemperature for an effective length of time. The hydrogenated amorphoussilicon coating is deposited by exposing the substrate to siliconhydride gas under pressure and elevated temperature for an effectivelength of time.

The hemispheric insulator 26 may be sized relative to the dome 37 suchthat a snug fit (i.e., hermetic seal) is achieved when assembled intothe cap 24. The hemispheric insulator 26 need not be perfectly symmetricor of classic hemispheric proportions. That is, the hemisphericinsulator 26 is substantially hemispheric, and may include, for example,slight adjustments in proportions, a modest flange (such as at the base)and other features as deemed appropriate. The hemispheric insulator 26is generally formed of homogeneous material, however, this is not arequirement. For example, the hemispheric insulator 26 may include anair or gas filled torus (not shown) therein to provide for desiredexpansion or compressibility.

As shown in FIG. 20, the electrode assembly 50 may be inserted into thetemplate (i.e., the formed blank 34) to provide for an embodiment of thecap 24 that includes a hemispheric hermetic seal.

As shown in FIG. 21, in various embodiments, a retainer 43 may be bondedor otherwise mated to a bottom of the cap 24 (i.e., a portion of the cap24 that faces to an interior of the housing 7 and faces the energystorage cell 12). The retainer 43 may be bonded to the cap 24 throughvarious techniques, such as aluminum welding (such as laser, ultrasonicand the like). Other techniques may be used for the bonding, includingfor example, stamping (i.e., mechanical bonding) and brazing. Thebonding may occur, for example, along a perimeter of the retainer 43.Generally, the bonding is provided for in at least one bonding point tocreate a desired seal 71. At least one fastener, such as a plurality ofrivets may be used to seal the insulator 26 within the retainer 43.

In the example of FIG. 21, the cap 24 is of a concave design (see FIG.12B). However, other designs may be used. For example, a convex cap 24may be provided (FIG. 12C), and an over-cap 24 may also be used (avariation of the embodiment of FIG. 12C, which is configured to mount asdepicted in FIG. 16C).

The material used for the cap as well as the feed-through 19 may beselected with regard for thermal expansion of the hemispheric insulator26. Further, manufacturing techniques may also be devised to account forthermal expansion. For example, when assembling the cap 24, amanufacturer may apply pressure to the hemispheric insulator 26, thus atleast somewhat compressing the hemispheric insulator 26. In this manner,there at least some thermal expansion of the cap 24 is provided forwithout jeopardizing efficacy of the hermetic seal.

For further clarification of the assembled ultracapacitor, refer to FIG.22, where a cut-away view of the ultracapacitor 10 is provided. In thisexample, the storage cell 12 is inserted into and contained within thebody 10. Each plurality of leads are bundled together and coupled to thehousing 7 as one of the terminals 8. In some embodiments, the pluralityof leads are coupled to a bottom of the body 10 (on the interior), thusturning the body 10 into a negative contact 55. Likewise, anotherplurality of leads are bundled and coupled to the feed-through 19, toprovide a positive contact 56. Electrical isolation of the negativecontact 55 and the positive contact 56 is preserved by the electricalinsulator 26. Generally, coupling of the leads is accomplished throughwelding, such as at least one of laser and ultrasonic welding. Ofcourse, other techniques may be used as deemed appropriate.

Inner Barrier

Referring now to FIG. 7, the housing 7 may include an inner barrier 30.In some embodiments, the barrier 30 is a coating. In this example, thebarrier 30 is formed of polytetrafluoroethylene (PTFE).Polytetrafluoroethylene (PTFE) exhibits various properties that makethis composition well suited for the barrier 30. PTFE has a meltingpoint of about 327 degrees Celsius, has excellent dielectric properties,has a coefficient of friction of between about 0.05 to 0.10, which isthe third-lowest of any known solid material, has a high corrosionresistance and other beneficial properties. Generally, an interiorportion of the cap 24 may include the barrier 30 disposed thereon.

Other materials may be used for the barrier 30. Among these othermaterials are forms of ceramics (any type of ceramic that may besuitably applied and meet performance criteria), other polymers(preferably, a high temperature polymer) and the like. Exemplary otherpolymers include perfluoroalkoxy (PFA) and fluorinated ethylenepropylene (FEP) as well as ethylene tetrafluoroethylene (ETFE).

The barrier 30 may include any material or combinations of materialsthat provide for reductions in electrochemical or other types ofreactions between the energy storage cell 12 and the housing 7 orcomponents of the housing 7. In some embodiments, the combinations aremanifested as homogeneous dispersions of differing materials within asingle layer. In other embodiments, the combinations are manifested asdiffering materials within a plurality of layers. Other combinations maybe used. In short, the barrier 30 may be considered as at least one ofan electrical insulator and chemically inert (i.e., exhibiting lowreactivity) and therefore substantially resists or impedes at least oneof electrical and chemical interactions between the storage cell 12 andthe housing 7. In some embodiments, the term “low reactivity” and “lowchemical reactivity” generally refer to a rate of chemical interactionthat is below a level of concern for an interested party.

In general, the interior of the housing 7 may be host to the barrier 30such that all surfaces of the housing 7 which are exposed to theinterior are covered. At least one untreated area 31 may be includedwithin the body 10 and on an outer surface 36 of the cap 24 (see FIG.8A). In some embodiments, untreated areas 31 (see FIG. 8B) may beincluded to account for assembly requirements, such as areas which willbe sealed or connected (such as by welding).

The barrier 30 may be applied to the interior portions usingconventional techniques. For example, in the case of PTFE, the barrier30 may be applied by painting or spraying the barrier 30 onto theinterior surface as a coating. A mask may be used as a part of theprocess to ensure untreated areas 31 retain desired integrity. In short,a variety of techniques may be used to provide the barrier 30.

In an exemplary embodiment, the barrier 30 is about 3 mil to about 5 milthick, while material used for the barrier 30 is a PFA based material.In this example, surfaces for receiving the material that make up thebarrier 30 are prepared with grit blasting, such as with aluminum oxide.Once the surfaces are cleaned, the material is applied, first as aliquid then as a powder. The material is cured by a heat treatingprocess. In some embodiments, the heating cycle is about 10 minutes toabout 15 minutes in duration, at temperatures of about 370 degreesCelsius. This results in a continuous finish to the barrier 30 that issubstantially free of pin-hole sized or smaller defects. FIG. 9 depictsassembly of an embodiment of the ultracapacitor 10 according to theteachings herein. In this embodiment, the ultracapacitor 10 includes thebody 10 that includes the barrier 30 disposed therein, a cap 24 with thebarrier 30 disposed therein, and the energy storage cell 12. Duringassembly, the cap 24 is set over the body 10. A first one of theterminals 8 is electrically coupled to the cap feed-through 19, while asecond one of the terminals 8 is electrically coupled to the housing 7,typically at the bottom, on the side or on the cap 24. In someembodiments, the second one of the terminals 8 is coupled to anotherfeed-through 19 (such as of an opposing cap 24).

With the barrier 30 disposed on the interior surface(s) of the housing7, electrochemical and other reactions between the housing 7 and theelectrolyte are greatly reduced or substantially eliminated. This isparticularly significant at higher temperatures where a rate of chemicaland other reactions is generally increased.

Notably, the leakage current for ultracapacitor 10 with a barrierindicates a comparably lower initial value and no substantial increaseover time while the leakage current for ultracapacitor 10 without abarrier indicates a comparably higher initial value as well as asubstantial increase over time.

Generally, the barrier 30 provides a suitable thickness of suitablematerials between the energy storage cell 12 and the housing 7. Thebarrier 30 may include a homogeneous mixture, a heterogeneous mixtureand/or at least one layer of materials. The barrier 30 may providecomplete coverage (i.e., provide coverage over the interior surface areaof the housing with the exception of electrode contacts) or partialcoverage. In some embodiments, the barrier 30 is formed of multiplecomponents.

Referring to FIG. 11, aspects of an additional embodiment are shown. Insome embodiments, the energy storage cell 12 is deposited within anenvelope 73. That is, the energy storage cell 12 has the barrier 30disposed thereon, wrapped thereover, or otherwise applied to separatethe energy storage cell 12 from the housing 7 once assembled. Theenvelope 73 may be applied well ahead of packaging the energy storagecell 12 into the housing 7. Therefore, use of an envelope 73 may presentcertain advantages, such as to manufacturers. (Note that the envelope 73is shown as loosely disposed over the energy storage cell 12 forpurposes of illustration).

In some embodiments, the envelope 73 is used in conjunction with thecoating, wherein the coating is disposed over at least a portion of theinterior surfaces. For example, in one embodiment, the coating isdisposed within the interior of the housing 7 only in areas where theenvelope 73 may be at least partially compromised (such as be aprotruding terminal 8). Together, the envelope 73 and the coating forman efficient barrier 30.

Accordingly, incorporation of the barrier 30 may provide for anultracapacitor that exhibits leakage current with comparatively lowinitial values and substantially slower increases in leakage currentover time in view of the prior art. Significantly, the leakage currentof the ultracapacitor remains at practical (i.e., desirably low) levelswhen the ultracapacitor is exposed to ambient temperatures for whichprior art capacitors would exhibit prohibitively large initial values ofleakage current and/or prohibitively rapid increases in leakage currentover time.

Having thus described embodiments of the barrier 30, and various aspectsthereof, it should be recognized the ultracapacitor 10 may exhibit otherbenefits as a result of reduced reaction between the housing 7 and theenergy storage media 1. For example, an effective series resistance(ESR) of the ultracapacitor 10 may exhibit comparatively lower valuesover time. Further, unwanted chemical reactions that take place in aprior art capacitor often create unwanted effects such as out-gassing,or in the case of a hermetically sealed housing, bulging of the housing.In both cases, this leads to a compromise of the structural integrity ofthe housing and/or hermetic seal of the capacitor. Ultimately, this maylead to leaks or catastrophic failure of the prior art capacitor. Insome embodiments, these effects may be substantially reduced oreliminated by the application of a disclosed barrier 30.

It should be recognized that the terms “barrier” and “coating” are notlimiting of the teachings herein. That is, any technique for applyingthe appropriate material to the interior of the housing 7, body 10and/or cap 24 may be used. For example, in other embodiments, thebarrier 30 is actually fabricated into or onto material making up thehousing body 10, the material then being worked or shaped as appropriateto form the various components of the housing 7. When considering someof the many possible techniques for applying the barrier 30, it may beequally appropriate to roll on, sputter, sinter, laminate, print, orotherwise apply the material(s). In short, the barrier 30 may be appliedusing any technique deemed appropriate by a manufacturer, designerand/or user.

Materials used in the barrier 30 may be selected according to propertiessuch as reactivity, dielectric value, melting point, adhesion tomaterials of the housing 7, coefficient of friction, cost, and othersuch factors. Combinations of materials (such as layered, mixed, orotherwise combined) may be used to provide for desired properties.

Using an enhanced housing 7, such as one with the barrier 30, may, insome embodiments, limit degradation of the advanced electrolyte system.While the barrier 30 presents one technique for providing an enhancedhousing 7, other techniques may be used. For example, use of a housing 7fabricated from aluminum would be advantageous, due to theelectrochemical properties of aluminum in the presence of electrolyte 6.However, given the difficulties in fabrication of aluminum, it has notbeen possible (until now) to construct embodiments of the housing 7 thattake advantage of aluminum.

Additional embodiments of the housing 7 include those that presentaluminum to all interior surfaces, which may be exposed to electrolyte,while providing users with an ability to weld and hermetically seal thehousing. Improved performance of the ultracapacitor 10 may be realizedthrough reduced internal corrosion, elimination of problems associatedwith use of dissimilar metals in a conductive media and for otherreasons. Advantageously, the housing 7 makes use of existing technology,such available electrode inserts that include glass-to-metal seals (andmay include those fabricated from stainless steel, tantalum or otheradvantageous materials and components), and therefore is economic tofabricate.

Although disclosed herein as embodiments of the housing 7 that aresuited for the ultracapacitor 10, these embodiments (as is the case withthe barrier 30) may be used with any type of energy storage deemedappropriate, and may include any type of technology practicable. Forexample, other forms of energy storage may be used, includingelectrochemical batteries, in particular, lithium based batteries.

In general, the material(s) exposed to an interior of the housing 7exhibit adequately low reactivity when exposed to the electrolyte 6,i.e., the advanced electrolyte system of the present invention, andtherefore are merely illustrative of some of the embodiments and are notlimiting of the teachings herein.

Factors for General Construction of Capacitors

An important aspect for consideration in construction of theultracapacitor 10 is maintaining good chemical hygiene. In order toassure purity of the components, in various embodiments, the activatedcarbon, carbon fibers, rayon, carbon cloth, and/or nanotubes making upthe energy storage media 1 for the two electrode 3, are dried atelevated temperature in a vacuum environment. The separator 5 is alsodried at elevated temperature in a vacuum environment. Once theelectrode 3 and the separator 5 are dried under vacuum, they arepackaged in the housing 7 without a final seal or cap in an atmospherewith less than 50 parts per million (ppm) of water. The uncappedultracapacitor 10 may be dried, for example, under vacuum over atemperature range of about 100 degrees Celsius to about 300 degreesCelsius. Once this final drying is complete, the electrolyte 6 may beadded and the housing 7 is sealed in a relatively dry atmosphere (suchas an atmosphere with less than about 50 ppm of moisture). Of course,other methods of assembly may be used, and the foregoing provides merelya few exemplary aspects of assembly of the ultracapacitor 10.

Supporting Methods of the Invention

Certain methods are provided herein for producing the ultracapacitorsthat may be utilized by the systems of the present invention, includingmethods of reducing impurities or fabricating devices of the presentinvention. Such methods of purification are also additionally applicableto any advanced electrolyte system of the present invention

i. AES Contaminants

In certain embodiments, the advanced electrolyte system (AES) of thepresent invention is purified remove contaminants and to provide desiredenhanced performance characteristics described herein. As such, thepresent disclosure provides a method for purifying an AES, the methodcomprising: mixing water into an advanced electrolyte system to providea first mixture; partitioning the first mixture; collecting the advancedelectrolyte system from the first mixture; adding a solvent to thecollected liquid to provide a second mixture; mixing carbon into thesecond mixture to provide a third mixture; separating the advancedelectrolyte system from the third mixture to obtain the purifiedadvanced electrolyte system. Generally, the process calls for selectingan electrolyte, adding de-ionized water as well as activated carbonunder controlled conditions. The de-ionized water and activated carbonare subsequently removed, resulting in an electrolyte that issubstantially purified. The purified electrolyte is suited for use in,among other things, an ultracapacitor.

This method may be used to ensure a high degree of purity of theadvanced electrolyte system (AES) of the present invention. It should benoted that although the process is presented in terms of specificparameters (such as quantities, formulations, times and the like), thatthe presentation is merely exemplary and illustrative of the process forpurifying electrolyte and is not limiting thereof.

For example, the method may further comprise one or more of thefollowing steps or characterizations: heating the first mixture; whereinpartitioning comprises letting the first mixture sit undisturbed untilthe water and the AES are substantially partitioned; wherein adding asolvent comprises adding at least one of diethylether, pentone,cyclopentone, hexane, cyclohexane, benzene, toluene, 1-4 dioxane, andchloroform; wherein mixing carbon comprises mixing carbon powder;wherein mixing carbon comprises stirring the third mixture substantiallyconstantly; wherein separating the AES comprises at least one offiltering carbon from the third mixture and evaporating the solvent fromthe third mixture.

In a first step of the process for purifying electrolyte, theelectrolyte 6 (in some embodiments, the ionic liquid) is mixed withdeionized water, and then raised to a moderate temperature for someperiod of time. In a proof of concept, fifty (50) milliliters (ml) ofionic liquid was mixed with eight hundred and fifty (850) milliliters(ml) of the deionized water. The mixture was raised to a constanttemperature of sixty (60) degrees Celsius for about twelve (12) hoursand subjected to constant stirring (of about one hundred and twenty(120) revolutions per minute (rpm)).

In a second step, the mixture of ionic liquid and deionized water ispermitted to partition. In this example, the mixture was transferred viaa funnel, and allowed to sit for about four (4) hours.

In a third step, the ionic liquid is collected. In this example, a waterphase of the mixture resided on the bottom, with an ionic liquid phaseon the top. The ionic liquid phase was transferred into another beaker.

In a fourth step, a solvent was mixed with the ionic liquid. In thisexample, a volume of about twenty five (25) milliliters (ml) of ethylacetate was mixed with the ionic liquid. This mixture was again raisedto a moderate temperature and stirred for some time.

Although ethyl acetate was used as the solvent, the solvent can be atleast one of diethylether, pentone, cyclopentone, hexane, cyclohexane,benzene, toluene, 1-4 dioxane, chloroform or any combination thereof aswell as other material(s) that exhibit appropriate performancecharacteristics. Some of the desired performance characteristics includethose of a non-polar solvent as well as a high degree of volatility.

In a fifth step, carbon powder is added to the mixture of the ionicliquid and solvent. In this example, about twenty (20) weight percent(wt %) of carbon (of about a 0.45 micrometer diameter) was added to themixture.

In a sixth step, the ionic liquid is again mixed. In this example, themixture with the carbon powder was then subjected to constant stirring(120 rpm) overnight at about seventy (70) degrees Celsius.

In a seventh step, the carbon and the ethyl acetate are separated fromthe ionic liquid. In this example, the carbon was separated usingBuchner filtration with a glass microfiber filter. Multiple filtrations(three) were performed. The ionic liquid collected was then passedthrough a 0.2 micrometer syringe filter in order to remove substantiallyall of the carbon particles. In this example, the solvent was thensubsequently separated from the ionic liquid by employing rotaryevaporation. Specifically, the sample of ionic liquid was stirred whileincreasing temperature from seventy (70) degrees Celsius to eighty (80)degrees Celsius, and finished at one hundred (100) degrees Celsius.Evaporation was performed for about fifteen (15) minutes at each of therespective temperatures.

The process for purifying electrolyte has proven to be very effective.For the sample ionic liquid, water content was measured by titration,with a titration instrument provided by Mettler-Toledo Inc., ofColumbus, Ohio (model No: AQC22). Halide content was measured with anISE instrument provided by Hanna Instruments of Woonsocket, R.I. (modelno. AQC22). The standards solution for the ISE instrument was obtainedfrom Hanna, and included HI 4007-03 (1,000 ppm chloride standard), HI4010-03 (1,000 ppm fluoride standard) HI 4000-00 (ISA for halideelectrodes), and HI 4010-00 (TISAB solution for fluoride electrodeonly). Prior to performing measurements, the ISE instrument wascalibrated with the standards solutions using 0.1, 10, 100 and 1,000parts per million (ppm) of the standards, mixed in with deionized water.ISA buffer was added to the standard in a 1:50 ratio for measurement ofCl— ions. Results are shown in Table 9.

TABLE 9 Purification Data for Electrolyte Containing1-butyl-1-methylpyrolidinium and tetracyanoborate Before After DI WaterImpurity (ppm) (ppm) (ppm) Cl⁻ 5,300.90 769 9.23E−1 F⁻ 75.61 10.611.10E−1 H₂0 1080 20 —

A four step process was used to measure the halide ions. First, Cl— andF— ions were measured in the deionized water. Next, a 0.01 M solution ofionic liquid was prepared with deionized water. Subsequently, Cl— and F—ions were measured in the solution. Estimation of the halide content wasthen determined by subtracting the quantity of ions in the water fromthe quantity of ions in the solution.

Purification standards were also examined with respect to theelectrolyte contaminant compositions through the analysis of leakagecurrent. Leakage current for purified electrolyte in a similarlystructured ultracapacitor 10 shows a substantial decrease in initialleakage current, as well as a modest decrease in leakage current overthe later portion of the measurement interval. More information isprovided on the construction of each embodiment in Table 10.

TABLE 10 Test Ultracapacitor Configuration Parameter Cell Size: Open SubC Open Sub C Casing: Coated P870 Coated P870 Electrode Double SidedActivated Double Sided Activated Material: Carbon(150/40) Carbon(150/40)Separator: Fiberglass Fiberglass Size of IE: 233 × 34 mm IE: 233 × 34 mmElectrodes: OE: 256 × 34 mm OE: 256 × 34 mm Tabs: 0.005″ Aluminum (3Tabs) 0.005″ Aluminum (3 Tabs) Temperature 150° C. 150° C. Electrolyte:Unpurified AES Purified AES

Other benefits are also realized, including improvements in stability ofresistance and capacitance of the ultracapacitor 10.

Leakage current may be determined in a number of ways. Qualitatively,leakage current may be considered as current drawn into a device, oncethe device has reached a state of equilibrium. In practice, it is alwaysor almost always necessary to estimate the actual leakage current as astate of equilibrium that may generally only be asymptoticallyapproached. Thus, the leakage current in a given measurement may beapproximated by measuring the current drawn into the ultracapacitor 10,while the ultracapacitor 10 is held at a substantially fixed voltage andexposed to a substantially fixed ambient temperature for a relativelylong period of time. In some instances, a relatively long period of timemay be determined by approximating the current time function as anexponential function, then allowing for several (e.g., about 3 to 5)characteristic time constants to pass. Often, such a duration rangesfrom about 50 hours to about 100 hours for many ultracapacitortechnologies. Alternatively, if such a long period of time isimpractical for any reason, the leakage current may simply beextrapolated, again, perhaps, by approximating the current time functionas an exponential or any approximating function deemed appropriate.Notably, leakage current will generally depend on ambient temperature.So, in order to characterize performance of a device at a temperature orin a temperature range, it is generally important to expose the deviceto the ambient temperature of interest when measuring leakage current.

Note that one approach to reduce the volumetric leakage current at aspecific temperature is to reduce the operating voltage at thattemperature. Another approach to reduce the volumetric leakage currentat a specific temperature is to increase the void volume of theultracapacitor. Yet another approach to reduce the leakage current is toreduce loading of the energy storage media 1 on the electrode 3.

Having disclosed aspects of embodiments for purification of electrolyteand ionic liquid, it should be recognized that a variety of embodimentsmay be realized. Further a variety of techniques may be practiced. Forexample, steps may be adjusted, the order of steps and the like.

ii. Water/Moisture Content and Removal

The housing 7 of a sealed ultracapacitor 10 may be opened, and thestorage cell 12 sampled for impurities. Water content may be measuredusing the Karl Fischer method for the electrodes, separator andelectrolyte from the cell 42. Three measurements may be taken andaveraged.

In general, a method for characterizing a contaminant within theultracapacitor includes breaching the housing 7 to access contentsthereof, sampling the contents and analyzing the sample. Techniquesdisclosed elsewhere herein may be used in support of the characterizing.

Note that to ensure accurate measurement of impurities in theultracapacitor and components thereof, including the electrode, theelectrolyte and the separator, assembly and disassembly may be performedin an appropriate environment, such as in an inert environment within aglove box.

By reducing the moisture content in the ultracapacitor 10 (e.g., to lessthan 500 part per million (ppm) over the weight and volume of theelectrolyte and the impurities to less than 1,000 ppm), theultracapacitor 10 can more efficiently operate over the temperaturerange, with a leakage current (I/L) that is less than 10 Amperes perLiter within that temperature range and voltage range.

In one embodiment, leakage current (I/L) at a specific temperature ismeasured by holding the voltage of the ultracapacitor 10 constant at therated voltage (i.e., the maximum rated operating voltage) for seventytwo (72) hours. During this period, the temperature remains relativelyconstant at the specified temperature. At the end of the measurementinterval, the leakage current of the ultracapacitor 10 is measured.

In some embodiments, a maximum voltage rating of the ultracapacitor 10is about 4 V at room temperature. An approach to ensure performance ofthe ultracapacitor 10 at elevated temperatures (for example, over 210degrees Celsius), is to derate (i.e., to reduce) the voltage rating ofthe ultracapacitor 10. For example, the voltage rating may be adjusteddown to about 0.5 V, such that extended durations of operation at highertemperature are achievable.

iii. Fabrication Techniques for Ultracapacitors

Moreover, it should be recognized that certain robust assemblytechniques may be required to provide highly efficient energy storage ofthe ultracapacitors described herein. Accordingly, some of thetechniques for assembly are now discussed.

Once the ultracapacitor 10 is fabricated, it may be used in hightemperature applications with little or no leakage current and littleincrease in resistance. The ultracapacitor 10 described herein canoperate efficiently at temperatures from about minus 40 degrees Celsiusto about 210 degrees Celsius with leakage currents normalized over thevolume of the device less than 10 amperes per liter (A/L) of volume ofthe device within the entire operating voltage and temperature range. Incertain embodiments, the capacitor is operable across temperatures fromminus 40 degrees Celsius to 210 degrees Celsius.

As an overview, a method of assembly of a cylindrically shapedultracapacitor 10 is provided. Beginning with the electrode 3, eachelectrode 3 is fabricated once the energy storage media 1 has beenassociated with the current collector 2. A plurality of leads are thencoupled to each electrode 3 at appropriate locations. A plurality ofelectrode 3 are then oriented and assembled with an appropriate numberof separators 5 therebetween to form the storage cell 12. The storagecell 12 may then be rolled into a cylinder, and may be secured with awrapper. Generally, respective ones of the leads are then bundled toform each of the terminals 8.

Prior to incorporation of the electrolyte 6, i.e., the advancedelectrolyte systems of the present invention, into the ultracapacitor 10(such as prior to assembly of the storage cell 12, or thereafter) eachcomponent of the ultracapacitor 10 may be dried to remove moisture. Thismay be performed with unassembled components (i.e., an empty housing 7,as well as each of the electrode 3 and each of the separators 5), andsubsequently with assembled components (such as the storage cell 12).

Drying may be performed, for example, at an elevated temperature in avacuum environment. Once drying has been performed, the storage cell 12may then be packaged in the housing 7 without a final seal or cap. Insome embodiments, the packaging is performed in an atmosphere with lessthan 50 parts per million (ppm) of water. The uncapped ultracapacitor 10may then be dried again. For example, the ultracapacitor 10 may be driedunder vacuum over a temperature range of about 100 degrees Celsius toabout 300 degrees Celsius. Once this final drying is complete, thehousing 7 may then be sealed in, for example, an atmosphere with lessthan 50 ppm of moisture.

In some embodiments, once the drying process (which may also be referredto a “baking” process) has been completed, the environment surroundingthe components may be filled with an inert gas. Exemplary gasses includeargon, nitrogen, helium, and other gasses exhibiting similar properties(as well as combinations thereof).

Generally, a fill port (a perforation in a surface of the housing 7) isincluded in the housing 7, or may be later added. Once theultracapacitor 10 has been filled with electrolyte 6, i.e., the advancedelectrolyte systems of the present invention, the fill port may then beclosed. Closing the fill port may be completed, for example, by weldingmaterial (e.g., a metal that is compatible with the housing 7) into orover the fill port. In some embodiments, the fill port may betemporarily closed prior to filling, such that the ultracapacitor 10 maybe moved to another environment, for subsequent re-opening, filling andclosure. However, as discussed herein, it is considered that theultracapacitor 10 is dried and filled in the same environment.

A number of methods may be used to fill the housing 7 with a desiredquantity of the advanced electrolyte system. Generally, controlling thefill process may provide for, among other things, increases incapacitance, reductions in equivalent-series-resistance (ESR), andlimiting waste of electrolyte. A vacuum filling method is provided as anon-limiting example of a technique for filling the housing 7 andwetting the storage cell 12 with the electrolyte 6.

First, however, note that measures may be taken to ensure that anymaterial that has a potential to contaminate components of theultracapacitor 10 is clean, compatible and dry. As a matter ofconvention, it may be considered that “good hygiene” is practiced toensure assembly processes and components do not introduce contaminantsinto the ultracapacitor 10.

In the “vacuum method” a container is placed onto the housing 7 aroundthe fill port. A quantity of electrolyte 6, i.e., the advancedelectrolyte systems of the present invention, is then placed into thecontainer in an environment that is substantially free of oxygen andwater (i.e., moisture). A vacuum is then drawn in the environment, thuspulling any air out of the housing and thus simultaneously drawing theelectrolyte 6 into the housing 7. The surrounding environment may thenbe refilled with inert gas (such as argon, nitrogen, or the like, orsome combination of inert gases), if desired. The ultracapacitor 10 maybe checked to see if the desired amount of electrolyte 6 has been drawnin. The process may be repeated as necessary until the desired amount ofelectrolyte 6 is in the ultracapacitor 10.

After filling with electrolyte 6, i.e., the advanced electrolyte systemsof the present invention, in certain embodiments, material may be fitinto the fill port to seal the ultracapacitor 10. The material may be,for example, a metal that is compatible with the housing 7 and theelectrolyte 6. In one example, material is force fit into the fill port,essentially performing a “cold weld” of a plug in the fill port. Inparticular embodiments, the force fit may be complimented with otherwelding techniques as discussed further herein.

In general, assembly of the housing often involves placing the storagecell 12 within the body 10 and filling the body 10 with the advancedelectrolyte system. Another drying process may be performed. Exemplarydrying includes heating the body 10 with the storage cell 12 andadvanced electrolyte system therein, often under a reduced pressure(e.g., a vacuum). Once adequate (optional) drying has been performed,final steps of assembly may be performed. In the final steps, internalelectrical connections are made, the cap 24 is installed, and the cap 24is hermetically sealed to the body 10, by, for example, welding the cap24 to the body 10.

In some embodiments, at least one of the housing 7 and the cap 24 isfabricated to include materials that include a plurality of layers. Forexample, a first layer of material may include aluminum, with a secondlayer of material being stainless steel. In this example, the stainlesssteel is clad onto the aluminum, thus providing for a material thatexhibits a desired combination of metallurgical properties. That is, inthe embodiments provided herein, the aluminum is exposed to an interiorof the energy storage cell (i.e., the housing), while the stainlesssteel is exposed to exterior. In this manner, advantageous electricalproperties of the aluminum are enjoyed, while structural properties (andmetallurgical properties, i.e., weldability) of the stainless steel arerelied upon for construction. The multi-layer material may includeadditional layers as deemed appropriate. Advantageously, this providesfor welding of stainless steel to stainless steel, a relatively simplewelding procedure.

While material used for construction of the body 10 includes aluminum,any type of aluminum or aluminum alloy deemed appropriate by a designeror fabricator (all of which are broadly referred to herein simply as“aluminum”). Various alloys, laminates, and the like may be disposedover (e.g., clad to) the aluminum (the aluminum being exposed to aninterior of the body 10. Additional materials (such as structuralmaterials or electrically insulative materials, such as somepolymer-based materials) may be used to compliment the body and/or thehousing 7. The materials disposed over the aluminum may likewise bechosen by what is deemed appropriate by a designer or fabricator.

Use of aluminum is not necessary or required. In short, materialselection may provide for use of any material deemed appropriate by adesigner, fabricator, or user and the like. Considerations may be givento various factors, such as, for example, reduction of electrochemicalinteraction with the electrolyte 6, structural properties, cost and thelike.

Embodiments of the ultracapacitor 10 that exhibit a relatively smallvolume may be fabricated in a prismatic form factor such that theelectrode 3 of the ultracapacitor 10 oppose one another, at least oneelectrode 3 having an internal contact to a glass to metal seal, theother having an internal contact to a housing or to a glass to metalseal.

A volume of a particular ultracapacitor 10 may be extended by combiningseveral storage cells (e.g., welding together several jelly rolls)within one housing 7 such that they are electrically in parallel or inseries.

In a variety of embodiments, it is useful to use a plurality of theultracapacitors 10 together to provide a power supply. In order toprovide for reliable operation, individual ultracapacitors 10 may betested in advance of use. In order to perform various types of testing,each of the ultracapacitors 10 may be tested as a singular cell, inseries or in parallel with multiple ultracapacitors 10 attached. Usingdifferent metals joined by various techniques (such as by welding) canreduce the ESR of the connection as well as increase the strength of theconnections. Some aspects of connections between ultracapacitors 10 arenow introduced.

In some embodiments, the ultracapacitor 10 includes two contacts. Thetwo contacts are the glass-to-metal seal pin (i.e., the feed-through 19)and the entire rest of the housing 7. When connecting a plurality of theultracapacitors 10 in series, it is often desired to couple aninterconnection between a bottom of the housing 7 (in the case of thecylindrical form housing 7), such that distance to the internal leads isminimized, and therefore of a minimal resistance. In these embodiments,an opposing end of the interconnection is usually coupled to the pin ofthe glass-to-metal seal.

With regard to interconnections, a common type of weld involves use of aparallel tip electric resistance welder. The weld may be made byaligning an end of the interconnection above the pin and welding theinterconnection directly to the pin. Using a number of welds willincrease the strength and connection between the interconnection and thepin. Generally, when welding to the pin, configuring a shape of the endof the interconnection to mate well with the pin serves to ensure thereis substantially no excess material overlapping the pin that would causea short circuit.

An opposed tip electric resistance welder may be used to weld theinterconnection to the pin, while an ultrasonic welder may used to weldthe interconnection to the bottom of the housing 7. Soldering techniquesmay used when metals involved are compatible.

With regard to materials used in interconnections, a common type ofmaterial used for the interconnection is nickel. Nickel may be used asit welds well with stainless steel and has a strong interface. Othermetals and alloys may be used in place of nickel, for example, to reduceresistance in the interconnection.

Generally, material selected for the interconnection is chosen forcompatibility with materials in the pin as well as materials in thehousing 7. Exemplary materials include copper, nickel, tantalum,aluminum, and nickel copper clad. Further metals that may be usedinclude silver, gold, brass, platinum, and tin.

In some embodiments, such as where the pin (i.e., the feed-through 19)is made of tantalum, the interconnection may make use of intermediatemetals, such as by employing a short bridge connection. An exemplarybridge connection includes a strip of tantalum, which has been modifiedby use of the opposed tip resistance welder to weld a strip ofaluminum/copper/nickel to the bridge. A parallel resistance welder isthen used to weld the tantalum strip to the tantalum pin.

The bridge may also be used on the contact that is the housing 7. Forexample, a piece of nickel may be resistance welded to the bottom of thehousing 7. A strip of copper may then be ultrasonic welded to the nickelbridge. This technique helps to decrease resistance of cellinterconnections. Using different metals for each connection can reducethe ESR of the interconnections between cells in series.

Having thus described aspects of a robust ultracapacitor 10 that isuseful for high temperature environments (i.e., up to about 210 degreesCelsius), some additional aspects are now provided and/or defined.

A variety of materials may be used in construction of the ultracapacitor10. Integrity of the ultracapacitor 10 is essential if oxygen andmoisture are to be excluded and the electrolyte 6 is to be preventedfrom escaping. To accomplish this, seam welds and any other sealingpoints should meet standards for hermiticity over the intendedtemperature range for operation. Also, materials selected should becompatible with other materials, such as ionic liquids and solvents thatmay be used in the formulation of the advanced electrolyte system.

In some embodiments, the feed-through 19 is formed of metal such as atleast one of KOVAR™ (a trademark of Carpenter Technology Corporation ofReading, Pa., where KOVAR is a vacuum melted, iron-nickel-cobalt, lowexpansion alloy whose chemical composition is controlled within narrowlimits to assure precise uniform thermal expansion properties), Alloy 52(a nickel iron alloy suitable for glass and ceramic sealing to metal),tantalum, molybdenum, niobium, tungsten, Stainless Steel 446 (aferritic, non-heat treatable stainless steel that offers good resistanceto high temperature corrosion and oxidation) and titanium.

The body of glass-to-metal seals that take advantage of the foregoingmay be fabricated from 300 series stainless steels, such as 304, 304L,316, and 316L alloys. The bodies may also be made from metal such as atleast one of various nickel alloys, such as Inconel (a family ofaustenitic nickel-chromium-based superalloys that are oxidation andcorrosion resistant materials well suited for service in extremeenvironments subjected to pressure and heat) and Hastelloy (a highlycorrosion resistant metal alloy that includes nickel and varyingpercentages of molybdenum, chromium, cobalt, iron, copper, manganese,titanium, zirconium, aluminum, carbon, and tungsten).

The insulating material between the feed-through 19 and the surroundingbody in the glass-to-metal seal is typically a glass, the composition ofwhich is proprietary to each manufacturer of seals and depends onwhether the seal is under compression or is matched. Other insulativematerials may be used in the glass-to-metal seal. For example, variouspolymers may be used in the seal. As such, the term “glass-to-metal”seal is merely descriptive of a type of seal, and is not meant to implythat the seal must include glass.

The housing 7 for the ultracapacitor 10 may be made from, for example,types 304, 304L, 316, and 316L stainless steels. They may also beconstructed from, but not limited to, some of the aluminum alloys, suchas 1100, 3003, 5052, 4043 and 6061. Various multi-layer materials may beused, and may include, for example, aluminum clad to stainless steel.Other non-limiting compatible metals that may be used include platinum,gold, rhodium, ruthenium and silver.

Specific examples of glass-to-metal seals that have been used in theultracapacitor 10 include two different types of glass-to-metal seals. Afirst one is from SCHOTT with a US location in Elmsford, N.Y. Thisembodiment uses a stainless steel pin, glass insulator, and a stainlesssteel body. A second glass-to-metal seal is from HERMETIC SEALTECHNOLOGY of Cincinnati, Ohio. This second embodiment uses a tantalumpin, glass insulator and a stainless steel body. Varying sizes of thevarious embodiments may be provided.

An additional embodiment of the glass-to-metal seal includes anembodiment that uses an aluminum seal and an aluminum body. Yet anotherembodiment of the glass-to-metal seal includes an aluminum seal usingepoxy or other insulating materials (such as ceramics or silicon).

A number of aspects of the glass-to-metal seal may be configured asdesired. For example, dimensions of housing and pin, and the material ofthe pin and housing may be modified as appropriate. The pin can also bea tube or solid pin, as well as have multiple pins in one cover. Whilethe most common types of material used for the pin are stainless steelalloys, copper cored stainless steel, molybdenum, platinum-iridium,various nickel-iron alloys, tantalum and other metals, somenon-traditional materials may be used (such as aluminum). The housing isusually formed of stainless steel, titanium and/or various othermaterials.

A variety of fastening techniques may be used in assembly of theultracapacitor 10. For example, and with regards to welding, a varietyof welding techniques may be used. The following is an illustrativelisting of types of welding and various purposes for which each type ofwelding may be used.

Ultrasonic welding may be used for, among other things: welding aluminumtabs to the current collector; welding tabs to the bottom clad cover;welding a jumper tab to the clad bridge connected to the glass-to-metalseal pin; and welding jelly roll tabs together. Pulse or resistancewelding may be used for, among other things: welding leads onto thebottom of the can or to the pin; welding leads to the current collector;welding a jumper to a clad bridge; welding a clad bridge to the terminal8; welding leads to a bottom cover. Laser welding may be used for, amongother things: welding a stainless steel cover to a stainless steel can;welding a stainless steel bridge to a stainless steel glass-to-metalseal pin; and welding a plug into the fill port. TIG welding may be usedfor, among other things: sealing aluminum covers to an aluminum can; andwelding aluminum seal into place. Cold welding (compressing metalstogether with high force) may be used for, among other things: sealingthe fillport by force fitting an aluminum ball/tack into the fill port.

iv. Certain Advantageous Embodiments of the Fabrication

Certain advantageous embodiments, which are not intended to be limitingare provided herein below.

In one particular embodiment, and referring to FIG. 23, components of anexemplary electrode 3 are shown. In this example, the electrode 3 willbe used as the negative electrode 3 (however, this designation isarbitrary and merely for referencing).

As may be noted from the illustration, at least in this embodiment, theseparator 5 is generally of a longer length and wider width than theenergy storage media 1 (and the current collector 2). By using a largerseparator 5, protection is provided against short circuiting of thenegative electrode 3 with the positive electrode 3. Use of additionalmaterial in the separator 5 also provides for better electricalprotection of the leads and the terminal 8.

Refer now to FIG. 24 which provides a side view of an embodiment of thestorage cell 12. In this example, a layered stack of energy storagemedia 1 includes a first separator 5 and a second separator 5, such thatthe electrode 3 are electrically separated when the storage cell 12 isassembled into a rolled storage cell 23. Note that the term “positive”and “negative” with regard to the electrode 3 and assembly of theultracapacitor 10 is merely arbitrary, and makes reference tofunctionality when configured in the ultracapacitor 10 and charge isstored therein. This convention, which has been commonly adopted in theart, is not meant to apply that charge is stored prior to assembly, orconnote any other aspect other than to provide for physicalidentification of different electrodes.

Prior to winding the storage cell 12, the negative electrode 3 and thepositive electrode 3 are aligned with respect to each other. Alignmentof the electrode 3 gives better performance of the ultracapacitor 10 asa path length for ionic transport is generally minimized when there is ahighest degree of alignment. Further, by providing a high degree ofalignment, excess separator 5 is not included and efficiency of theultracapacitor 10 does not suffer as a result.

Referring now also to FIG. 25, there is shown an embodiment of thestorage cell 12 wherein the electrode 3 have been rolled into the rolledstorage cell 23. One of the separators 5 is present as an outermostlayer of the storage cell 12 and separates energy storage media 1 froman interior of the housing 7.

“Polarity matching” may be employed to match a polarity of the outermostelectrode in the rolled storage cell 23 with a polarity of the body 10.For example, in some embodiments, the negative electrode 3 is on theoutermost side of the tightly packed package that provides the rolledstorage cell 23. In these embodiments, another degree of assuranceagainst short circuiting is provided. That is, where the negativeelectrode 3 is coupled to the body 10, the negative electrode 3 is theplaced as the outermost electrode in the rolled storage cell 23.Accordingly, should the separator 5 fail, such as by mechanical wearinduced by vibration of the ultracapacitor 10 during usage, theultracapacitor 10 will not fail as a result of a short circuit betweenthe outermost electrode in the rolled storage cell 23 and the body 10.

For each embodiment of the rolled storage cell 23, (see for example,FIG. 25) a reference mark 72 may be in at least the separator 5. Thereference mark 72 will be used to provide for locating the leads on eachof the electrode 3. In some embodiments, locating of the leads isprovided for by calculation. For example, by taking into account aninner diameter of the jelly roll and an overall thickness for thecombined separators 5 and electrode 3, a location for placement of eachof the leads may be estimated. However, practice has shown that it ismore efficient and effective to use a reference mark 72. The referencemark 72 may include, for example, a slit in an edge of the separator(s)5.

Generally, the reference mark 72 is employed for each new specificationof the storage cell 12. That is, as a new specification of the storagecell 12 may call for differing thickness of at least one layer therein(over a prior embodiment), use of prior reference marks may be at leastsomewhat inaccurate.

In general, the reference mark 72 is manifested as a single radial linethat traverses the roll from a center thereof to a periphery thereof.Accordingly, when the leads are installed along the reference mark 72,each lead will align with the remaining leads. However, when the storagecell 12 is unrolled (for embodiments where the storage cell 12 is orwill become a roll), the reference mark 72 may be considered to be aplurality of markings (as shown in FIG. 26). As a matter of convention,regardless of the embodiment or appearance of marking of the storagecell 12, identification of a location for incorporation of the lead isconsidered to involve determination of a “reference mark 72” or a “setof reference marks 72.”

Referring now to FIG. 26, once the reference mark 72 has beenestablished (such as by marking a rolled up storage cell 12), aninstallation site for installation each of the leads is provided (i.e.,described by the reference mark 72). Once each installation site hasbeen identified, for any given build specification of the storage cell12, the relative location of each installation site may be repeated foradditional instances of the particular build of storage cell 12.

Generally, each lead is coupled to a respective current collector 2 inthe storage cell 12. In some embodiments, both the current collector 2and the lead are fabricated from aluminum. Generally, the lead iscoupled to the current collector 2 across the width, W, however, thelead may be coupled for only a portion of the width, W. The coupling maybe accomplished by, for example, ultrasonic welding of the lead to thecurrent collector 2. In order to accomplish the coupling, at least someof the energy storage media 1 may be removed (as appropriate) such thateach lead may be appropriately joined with the current collector 2.Other preparations and accommodations may be made, as deemedappropriate, to provide for the coupling.

In certain embodiments, opposing reference marks 73 may be included.That is, in the same manner as the reference marks 72 are provided, aset of opposing reference marks 73 may be made to account forinstallation of leads for the opposing polarity. That is, the referencemarks 72 may be used for installing leads to a first electrode 3, suchas the negative electrode 3, while the opposing reference marks 73 maybe used for installing leads to the positive electrode 3. In theembodiment where the rolled storage cell 23 is cylindrical, the opposingreference marks 73 are disposed on an opposite side of the energystorage media 1, and offset lengthwise from the reference marks 72 (asdepicted).

Note that in FIG. 26, the reference marks 72 and the opposing referencemarks 73 are both shown as being disposed on a single electrode 3. Thatis, FIG. 23 depicts an embodiment that is merely for illustration ofspatial (i.e., linear) relation of the reference marks 72 and theopposing reference marks 73. This is not meant to imply that thepositive electrode 3 and the negative electrode 3 share energy storagemedia 1. However, it should be noted that in instances where thereference marks 72 and the opposing reference marks 73 are placed byrolling up the storage cell 12 and then marking the separator 5, thatthe reference marks 72 and the opposing reference marks 73 may indeed byprovided on a single separator 5. However, in practice, only one set ofthe reference marks 72 and the opposing reference marks 73 would be usedto install the leads for any given electrode 3. That is, it should berecognized that the embodiment depicted in FIG. 26 is to be complimentedwith another layer of energy storage media 1 for another electrode 3which will be of an opposing polarity.

As shown in FIG. 27, the foregoing assembly technique results in astorage cell 12 that includes at least one set of aligned leads. A firstset of aligned leads 91 are particularly useful when coupling the rolledstorage cell 23 to one of the negative contact 55 and the positivecontact 56, while a set of opposing aligned leads 92 provide forcoupling the energy storage media 1 to an opposite contact (55, 56).

The rolled storage cell 23 may be surrounded by a wrapper 93. Thewrapper 93 may be realized in a variety of embodiments. For example, thewrapper 93 may be provided as KAPTON™ tape (which is a polyimide filmdeveloped by DuPont of Wilmington Del.), or PTFE tape. In this example,the KAPTON™ tape surrounds and is adhered to the rolled storage cell 23.The wrapper 93 may be provided without adhesive, such as a tightlyfitting wrapper 93 that is slid onto the rolled storage cell 23. Thewrapper 93 may be manifested more as a bag, such as one that generallyengulfs the rolled storage cell 23 (e.g., such as the envelope 83 ofFIG. 11, discussed above). In some of these embodiments, the wrapper 93may include a material that functions as a shrink-wrap would, andthereby provides an efficient physical (and in some embodiments,chemical) enclosure of the rolled storage cell 23. Generally, thewrapper 93 is formed of a material that does not interfere withelectrochemical functions of the ultracapacitor 10. The wrapper 93 mayalso provide partial coverage as needed, for example, to aid insertionof the rolled storage cell 23.

In some embodiments, the negative leads and the positive leads arelocated on opposite sides of the rolled storage cell 23 (in the case ofa jelly-roll type rolled storage cell 23, the leads for the negativepolarity and the leads for the positive polarity may be diametricallyopposed). Generally, placing the leads for the negative polarity and theleads for the positive polarity on opposite sides of the rolled storagecell 23 is performed to facilitate construction of the rolled storagecell 23 as well as to provide improved electrical separation.

In some embodiments, once the aligned leads 91, 92 are assembled, eachof the plurality of aligned leads 91, 92 are bundled together (in place)such that a shrink-wrap (not shown) may be disposed around the pluralityof aligned leads 91, 92. Generally, the shrink-wrap is formed of PTFE,however, any compatible material may be used.

In some embodiments, once shrink-wrap material has been placed about thealigned leads 91, the aligned leads 91 are folded into a shape to beassumed when the ultracapacitor 10 has been assembled. That is, withreference to FIG. 28, it may be seen that the aligned leads assume a “Z”shape. After imparting a “Z-fold” into the aligned leads 91, 92 andapplying the shrink-wrap, the shrink-wrap may be heated or otherwiseactivated such that the shrink-wrap shrinks into place about the alignedleads 91, 92. Accordingly, in some embodiments, the aligned leads 91, 92may be strengthened and protected by a wrapper. Use of the Z-fold isparticularly useful when coupling the energy storage media 1 to thefeed-through 19 disposed within the cap 24.

Additionally, other embodiments for coupling each set of aligned leads91, 92 (i.e., each terminal 8) to a respective contact 55, 56 may bepracticed. For example, in one embodiment, an intermediate lead iscoupled to the one of the feed-through 19 and the housing 7, such thatcoupling with a respective set of aligned leads 91, 92 is facilitated.

Furthermore, materials used may be selected according to properties suchas reactivity, dielectric value, melting point, adhesion to othermaterials, weldability, coefficient of friction, cost, and other suchfactors. Combinations of materials (such as layered, mixed, or otherwisecombined) may be used to provide for desired properties.

v. Particular Ultracapacitor Embodiments

Physical aspects of an exemplary ultracapacitor 10 of the presentinvention are shown below. Note that in the following tables, theterminology “tab” generally refers to the “lead” as discussed above; theterms “bridge” and “jumper” also making reference to aspects of the lead(for example, the bridge may be coupled to the feed-through, or “pin,”while the jumper is useful for connecting the bridge to the tabs, orleads). Use of various connections may facilitate the assembly process,and take advantage of certain assembly techniques. For example, thebridge may be laser welded or resistance welded to the pin, and coupledwith an ultrasonic weld to the jumper.

TABLE 10 Weights of Complete Cell With Electrolyte Weight PercentComponent (grams) of total SS Can (body of the housing) 14.451  20.87%SS Top cover (cap) 5.085  7.34% Tantalum glass-metal Seal 12.523  18.09%SS/Al Clad Bottom 10.150  14.66% Tack (seal for fill hole) 0.200  0.29%Inner Electrode (cleared, no tabs) 3.727  5.38% Inner Electrode Aluminum1.713  2.47% Inner Electrode Carbon 2.014  2.91% Outer Electrode(cleared, no tabs) 4.034  5.83% Outer Electrode Aluminum 1.810  2.61%Outer Electrode Carbon 2.224  3.21% Separator 1.487  2.15% Alum. Jellyroll Tabs (all 8) 0.407  0.59% Ta/Al clad bridge 0.216  0.31% Alum.Jumper (bridge-JR tabs) 0.055  0.08% Teflon heat shrink 0.201  0.29% AES16.700  24.12% Total Weight 69.236 100.00%

TABLE 11 Weights of Complete Cell Without Electrolyte Weight PercentComponent (grams) of total SS Can 14.451  27.51% SS Top cover 5.085 9.68% Tantalum glass-metal Seal 12.523  23.84% SS/Al Clad Bottom 10.150 19.32% Tack 0.200  0.38% Inner Electrode (cleared, no tabs) 3.727 7.09% Outer Electrode (cleared, no tabs) 4.034  7.68% Separator 1.487 2.83% Alum. Jelly roll Tabs (all 8) 0.407  0.77% Ta/Al clad bridge0.216  0.41% Alum. Jumper (bridge-JR tabs) 0.055  0.10% Teflon heatshrink 0.201  0.38% Total Weight 52.536 100.00%

TABLE 12 Weights of Cell Components in Full Cell with Electrolyte WeightPercent Component (grams) of total Can, covers, seal, bridge, 42.881 61.93% jumper, heat shrink, tack Jelly Roll with Electrodes, 9.655 13.95% tabs, separator Electrolyte 16.700  24.12% Total Weight 69.236100.00%

TABLE 13 Weights of Electrode Weight Percent of Component (grams) totalInner electrode carbon 2.014  25.95% Inner electrode aluminum 1.713 22.07% Outer electrode carbon 2.224  28.66% Outer electrode aluminum1.810  23.32% Total Weight 7.761 100.00%

Generally, the ultracapacitor 10 may be used under a variety ofenvironmental conditions and demands. For example, terminal voltage mayrange from about 100 mV to 10 V. Ambient temperatures may range fromabout minus 40 degrees Celsius to plus 210 degrees Celsius. Typical hightemperature ambient temperatures range from plus 60 degrees Celsius toplus 210 degrees Celsius.

Tables 14 and 15 provide comparative performance data for theseembodiments of the ultracapacitor 10. The performance data was collectedfor a variety of operating conditions as shown.

TABLE 14 Comparative Performance Data Temperature Voltage Time ESRInitial % ESR Capacitance % Capacitance Cell Weight Ending current Cell# (° C.) (V) (Hrs) (mOhm) Increase Initial (F) Decrease (g) (mA)D2011-09 150 1.25 1500 30 0 93 5 — 0.5 C1041-02 150 1.5 1150 45 60 32 —28.35 0.5 C2021-01 150 1.5 1465 33 100 32 70 26.61 0.8 D5311-01 150 1.6150 9 10 87 4 — 5 C6221-05 150 1.75 340 15 50 — — 38.31 1 C6221-05 1501.75 500 15 100 — — 38.31 2 C6221-05 150 1.75 600 15 200 — — 38.31 2C6221-05 150 1.75 650 15 300 — — 38.31 2 D1043-02 150 1.75 615 43 50 100— — 3 D1043-02 150 1.75 700 43 100 100 — — 3 C5071-01 150 1.75 600 26100 27 32 — 2 C5071-01 150 1.75 690 26 200 27 35 — 2 C5071-01 150 1.75725 26 300 27 50 — 2 C8091-06 125 1.75 500 38 5 63 11 37.9 0.5 C9021-02125 1.75 1250 37 10 61 — 39.19 0.3 D5011-02 125 1.9 150 13 0 105 0 — 1.4C8091-06 125 2 745 41 22 56 37.9 1.2 D2011-08 175 1 650 33 12 89 30 — 4D1043-10 175 1.3 480 30 100 93 50 — 6.5 C2021-04 175 1.4 150 35 100 27 —27.17 3.5 C4041-04 210 0.5 10 28 0 32 — 28.68 1 C4041-04 210 0.5 20 28 032 — 28.68 7 C4041-04 210 0.5 50 28 100 32 — 28.68 18

TABLE 15 Comparative Performance Data ESR Initial Leakage VolumetricVolumetric Volumetric % Capac-

Voltage Time Initial Capacitance Current ESR Capacitance Leakage Current% ESR itance Volume Cell # ° C. (V) (Hrs) (mOhm) (F) (mA) (Ohms × cc)(F/cc) (mA/cc) Increase Decrease (cc) D2011-09 150 1.25 1500 30 93 0.50.75 3.72 0.02 0 5 25 C2021- 01 150 1.5 1465 33 32 0.75 0.396 2.67 0.06100 5 12 C5071- 01 150 1.75 600 26 27 2 0.338 2.08 0.15 100 32 13C5071-01 150 1.75 690 26 27 2 0.338 2.08 0.15 200 35 13 C5071-01 1501.75 725 26 27 2 0.338 2.08 0.15 300 50 13 C8091-06 125 1.75 500 38 630.5 0.494 4.85 0.04 5 11 13 C9021-02 125 1.75 1250 37 61 0.25 0.481 4.690.02 10 11 13 D2011-08 175 1 650 33 89 4 0.825 3.56 0.16 12 30 25D1043-10 175 1.3 480 30 93 6.5 0.75 3.72 0.26 100 50 25 C4041-04 210 0.550 28 32 18 0.336 2.67 1.50 100 50 12

indicates data missing or illegible when filed

Thus, data provided in Tables 14 and 15 demonstrate that the teachingsherein enable performance of ultracapacitors in extreme conditions.Ultracapacitors fabricated accordingly may, for example, exhibit leakagecurrents of less than about 1 mA per milliliter of cell volume, and anESR increase of less than about 100 percent in 500 hours (while held atvoltages of less than about 2 V and temperatures less than about 150degrees Celsius). As trade-offs may be made among various demands of theultracapacitor (for example, voltage and temperature) performanceratings for the ultracapacitor may be managed (for example, a rate ofincrease for ESR, capacitance, etc) may be adjusted to accommodate aparticular need. Note that in reference to the foregoing, “performanceratings” is given a generally conventional definition, which is withregard to values for parameters describing conditions of operation.

Another exemplary ultracapacitor tested included an AES comprising1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Another exemplary ultracapacitor tested included an AES comprising1-ethyl-3-methylimidazolium tetrafluoroborate.

Another exemplary ultracapacitor tested included an AES comprising1-ethyl-3-methylimidazolium tetracyanoborate.

Another exemplary ultracapacitor tested included an AES comprising1-hexyl-3-methylimidazolium tetracyanoborate.

Another exemplary ultracapacitor tested included an AES comprising1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

Another exemplary ultracapacitor tested included an AES comprising1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate.

Another exemplary ultracapacitor tested included an AES comprising1-butyl-1-methylpyrrolidinium tetracyanoborate.

Another exemplary ultracapacitor tested included an AES comprising1-butyl-3-methylimidazolium trifluoromethanesulfonate.

Another exemplary ultracapacitor tested included an AES comprising1-ethyl-3-methylimidazolium tetracyanoborate.

Another exemplary ultracapacitor tested included an AES comprising1-ethyl-3-methylimidazolium and 1-butyl-1-methylpyrrolidinium andtetracyanoborate.

Another exemplary ultracapacitor tested included an AES comprising1-butyl-1-methylpyrrolidinium and tetracyanoborate and ethyl isopropylsulfone.

Note that measures of capacitance as well as ESR, as presented in Table9 and elsewhere herein, followed generally known methods. Considerfirst, techniques for measuring capacitance.

Capacitance may be measured in a number of ways. One method involvesmonitoring the voltage presented at the capacitor terminals while aknown current is drawn from (during a “discharge”) or supplied to(during a “charge”) of the ultracapacitor. More specifically, we may usethe fact that an ideal capacitor is governed by the equation:

I═C*dV/dt,

where I represents charging current, C represents capacitance and dV/dtrepresents the time-derivative of the ideal capacitor voltage, V. Anideal capacitor is one whose internal resistance is zero and whosecapacitance is voltage-independent, among other things. When thecharging current, I, is constant, the voltage V is linear with time, sodV/dt may be computed as the slope of that line, or as DeltaV/DeltaT.However, this method is generally an approximation and the voltagedifference provided by the effective series resistance (the ESR drop) ofthe capacitor should be considered in the computation or measurement ofa capacitance. The effective series resistance (ESR) may generally be alumped element approximation of dissipative or other effects within acapacitor. Capacitor behavior is often derived from a circuit modelcomprising an ideal capacitor in series with a resistor having aresistance value equal to the ESR. Generally, this yields goodapproximations to actual capacitor behavior.

In one method of measuring capacitance, one may largely neglect theeffect of the ESR drop in the case that the internal resistance issubstantially voltage-independent, and the charging or dischargingcurrent is substantially fixed. In that case, the ESR drop may beapproximated as a constant and is naturally subtracted out of thecomputation of the change in voltage during said constant-current chargeor discharge. Then, the change in voltage is substantially a reflectionof the change in stored charge on the capacitor. Thus, that change involtage may be taken as an indicator, through computation, of thecapacitance.

For example, during a constant-current discharge, the constant current,I, is known. Measuring the voltage change during the discharge, DeltaV,during a measured time interval DeltaT, and dividing the current value Iby the ratio DeltaV/DeltaT, yields an approximation of the capacitance.When I is measured in amperes, DeltaV in volts, and DeltaT in seconds,the capacitance result will be in units of Farads.

Turning to estimation of ESR, the effective series resistance (ESR) ofthe ultracapacitor may also be measured in a number of ways. One methodinvolves monitoring the voltage presented at the capacitor terminalswhile a known current is drawn from (during a “discharge”) or suppliedto (during a “charge”) the ultracapacitor. More specifically, one mayuse the fact that ESR is governed by the equation:

V=I*R,

where/represents the current effectively passing through the ESR, Rrepresents the resistance value of the ESR, and V represents the voltagedifference provided by the ESR (the ESR drop). ESR may generally be alumped element approximation of dissipative or other effects within theultracapacitor. Behavior of the ultracapacitor is often derived from acircuit model comprising an ideal capacitor in series with a resistorhaving a resistance value equal to the ESR. Generally, this yields goodapproximations of actual capacitor behavior.

In one method of measuring ESR, one may begin drawing a dischargecurrent from a capacitor that had been at rest (one that had not beencharging or discharging with a substantial current). During a timeinterval in which the change in voltage presented by the capacitor dueto the change in stored charge on the capacitor is small compared to themeasured change in voltage, that measured change in voltage issubstantially a reflection of the ESR of the capacitor. Under theseconditions, the immediate voltage change presented by the capacitor maybe taken as an indicator, through computation, of the ESR.

For example, upon initiating a discharge current draw from a capacitor,one may be presented with an immediate voltage change DeltaV over ameasurement interval DeltaT. So long as the capacitance of thecapacitor, C, discharged by the known current, I, during the measurementinterval, DeltaT, would yield a voltage change that is small compared tothe measured voltage change, DeltaV, one may divide DeltaV during thetime interval DeltaT by the discharge current, I, to yield anapproximation to the ESR. When I is measured in amperes and DeltaV involts, the ESR result will have units of Ohms.

Both ESR and capacitance may depend on ambient temperature. Therefore, arelevant measurement may require the user to subject the ultracapacitor10 to a specific ambient temperature of interest during the measurement.

Performance requirements for leakage current are generally defined bythe environmental conditions prevalent in a particular application. Forexample, with regard to a capacitor having a volume of 20 mL, apractical limit on leakage current may fall below 100 mA. Nominal valuesof normalized parameters may be obtained by multiplying or dividing thenormalized parameters (e.g. volumetric leakage current) by a normalizingcharacteristic (e.g. volume). For instance, the nominal leakage currentof an ultracapacitor having a volumetric leakage current of 10 mA/cc anda volume of 50 cc is the product of the volumetric leakage current andthe volume, 500 mA. Meanwhile the nominal ESR of an ultracapacitorhaving a volumetric ESR of 20 mOhm·cc and a volume of 50 cc is thequotient of the volumetric ESR and the volume, 0.4 mOhm

High Performance Ultracapacitors.

Although a number of exemplary ultracapacitors have been described it isto be understood that in some embodiments, other suitableultracapacitors may be used. For example, some embodiments may includeone or more of the ultracapacitors (or components thereof, relatedtechniques, etc.) described in International Publication No.PCT/US14/59971 filed Oct. 9, 2014, the entire contents of which areincorporated herein by reference.

For example, as described in the reference incorporated above, variousembodiments may include ultracapacitors that include an ionic liquid andat least one additive that decreases the rate of degradation of theionic liquid when the ultracapacitor is operating. For example, theadditive may be gelling agent. Some embodiments may include capacitorsthat employ a solid state electrolyte. In some such embodiments, theultracapacitor may operate without the use of a separator.

Various embodiments may include ultracapacitors that include anelectrode of the type described in U.S. Provisional Patent ApplicationSerial No. 62/061,947, filed Oct. 9, 2014. The electrode may include acurrent collector comprising aluminum with a carbide (e.g., aluminumcarbide) layer on at least one surface, on which at least one layer ofCNTs is disposed. The electrode may comprise vertically-aligned,horizontally-aligned, or nonaligned (e.g., tangled or clustered) CNTs.The electrode may comprise compressed CNTs. The electrode may comprisesingle-walled, double-walled, or multiwalled CNTs. The electrode maycomprise multiple layers of CNTs. In some embodiments the aluminumcarbide layer may include whisker-like protrusions of carbide material,on which CNTs may be disposed (e.g., in a conformal manner).

Ultracapacitors of the type described above may perform advantageouslyin downhole conditions. For example, in some embodiments, suchultracapacitors may, for example, operate at temperatures as high as 210degrees Celsius, 225 degrees Celsius, 250 degrees Celsius, or more for10,000 charge/discharge cycles and/or over 100 hours or more at avoltage of 0.5V or more while exhibiting and increase in ESR or lessthan 100%, e.g. less than about 85% and a decrease in capacitance ofless than about 10%. In some embodiments, such ultracapacitors may havea volumetric capacitance of about 5 Farad per liter (F/L), 6 F/L, 7 F/L,8 F/L, 8 F/L, 10 F/L or more, e.g., in the range of about 1 to about 10F/L or any sub-range thereof.

In some embodiments, ultracapacitors of the types described herein mayexhibit any of: a high volumetric energy density (e.g., exceeding 5Wh/L, 6 Wh/L, 7 Wh/L, 8 Wh/L, 9 Wh/L, 10 Wh/L. 11 Wh/L, 12 Wh/L, 15Wh/L, 18 Wh/L, 20 Wh/L, or more), a high gravimetric energy density(e.g., exceeding 5 Wh/kg, 6 Wh/kg, 7 Wh/kg, 8 Wh/kg, 9 Wh/kg, 10 Wh/kg.11 Wh/kg, 12 Wh/kg, 15 Wh/kg, 18 Wh/kg, or more), a high volumetricpower density (e.g., exceeding 30 kW/L, 40 kW/L, 50 kW/L, 60 kW/L, 70kW/L, 80 kW/L, 90 kW/L, 100 kW/L, 110 kW/L, 120 kW/L, or more), a highgravimetric power density (e.g., exceeding 30 kW/kg, 40 kW/kg, 50 kW/kg,60 kW/kg, 70 kW/kg, 80 kW/kg, 90 kW/kg, 100 kW/kg, 110 kW/kg, 120 kw/KGor more), and combinations thereof. In some embodiments, ultracapacitorsof the types described herein demonstrate high performance as indicatedby the product of energy density and power density, e.g., exceeding 300Wh-kW/L², 500 Wh-kW/L², 700 Wh-kW/L², or more. For example, theultracapacitors disclosed herein are capable of maintaining theirperformance over a long period of time, e.g., hundreds of thousands, oreven millions of charge/discharge cycles.

Power Systems for Use with Downhole Toolstring Power Bus

In some embodiments, the methods and apparatus described herein mayprovide power downhole in environments that have temperatures rangingfrom as low as −40 degrees Celsius to up to about 200 degrees Celsius orhigher, including up to about 300 degrees Celsius. Some embodimentsprovide power generation capabilities as well as energy storage, and canthus provide power for extended durations of operation in harshenvironments. Some embodiments are be economical to own and maintain.

As shown in FIG. 1 above, downhole instrumentation is typicallyorganized into a toolstring in which various downhole instruments, ortools, are connected to each other, usually in series. The downholetools may be electrically connected to each other to each other tocommunicate with each other and/or to provide electrical power to eachtool in the toolstring. Various methods of electrically connecting toolsto each other may be used, e.g., the MSID based electrical connectionsof the type described herein. Such electrical connections are generallyreferred to herein as a toolstring power bus, or “′TPB.”

In some embodiments, tools connected to the TPB obtain electrical powerfrom one or more power sources connected to the TPB. In other words, theTPB distributes power from a source or sources to the individual toolsin the string.

The power source may be a downhole source such as a downhole generatoror a battery. In some embodiments, the power source may be a topsideelectrical power source located on the surface, provided there is asuitable electrical connection between the topside source and thedownhole tool string.

In various embodiments, the power source feeding the TPB may not be ableto meet the peak power requirements of certain types of downholeinstruments. Disclosed herein are power systems that overcome suchlimitations.

The power systems disclosed herein may include energy storage devices(ESDs), particularly high temperature rechargeable energy storagedevices (HIRESD's), disposed at certain locations along the tool stringto provide power to certain tools in the toolstring. The ESDs disclosedherein are capable of meeting peak power requirements of one or morecorresponding tools in the toolstring.

For example, the ESD may provide power to such tools as a nuclearmagnetic resonance tool, a coring tool, a sonic tool, a neutron densitytool, a gamma detector tool a seismic measurement tool, a telemetry tool(e.g., an EM or mud pulse telemetry tool) a resistivity tool, aformation tester, or any other tool with high peak power requirements.

In certain embodiments, the ESDs are HTRESDs that are capable ofoperating at the temperatures found in the downhole environment. Incertain embodiments the HTRESDs include ultracapacitors capable ofoperating over a wide range of temperatures e.g., between about −40degrees Celsius up to about 250 degrees Celsius, or even highertemperatures under certain conditions. Specific examples of HTRESDs,particularly ultracapacitors, of the present invention are disclosedherein, and in PCT Publication No. WO2013009720 published Jan. 17, 2013.PCT Publication No. WO2013126915 published Aug. 29, 2013, PCTPublication No. WO2014145259 published Sep. 18, 2014, PCT PublicationNo. WO2014145520 published Sep. 18, 2014, and International PublicationNo. PCT/US14/59971 filed Oct. 9, 2014, each of which is incorporatedherein by reference in its entirety.

A great compliment of components may also be powered by the powersystems disclosed herein. In certain embodiments the ESDs, includingHTRESDs and ultracapacitors, will be connected at various locations in atoolstring in order to provide the peak power demand of variousinstruments including, for example: resistivity sensors, nuclear sensorsincluding pulsed neutron and gamma sensors, nuclear magnetic resonancesensors such as magnetic resonance imaging sensors, acoustic sensors,coring devices, seismic sensors, telemetry devices, devices forimplementing various sampling protocols, geosteering devices, devicesfor communications, data processing, data storage, and any suitablecombination thereof. In some embodiments, each ESD provides power to asingle tool or tool module. In other embodiments, one ESD may providepower to multiple tools or tool modules (e.g., one upstring module andone downstring module).

According to various embodiments, the power system disclosed herein maybe used with any tool having an instantaneous power requirement, alsoreferred to herein as peak power demand or requirement, which cannot beprovided by other power sources (e.g., a downhole battery or generator)connected to the TPB. In certain embodiments, the power systemsdisclosed herein provide a peak power ranging from one tenth (0.10) of aWatt to about one hundred megaWatts (MW) or any sub-range thereof. Incertain embodiments, the ESDs disclosed herein, including HTRESDs andultracapacitors, may have an initial peak power density in the range of0.01 w/L to 150 kW/L, or any sub-range thereof. In certain embodiments,a number of ESDs, e.g., HTRESDs including ultracapacitors, are arranged,e.g., in series, to provide a power system with the desired performancecharacteristics, e.g., peak operating current, voltage, and power,necessary for operation of the associated tools in the toolstring.

In some embodiments the ESDs are capable of being recharged at leastonce to provide multiple charging and discharging cycles. Thus, anassociated downhole instrument may be used multiple times during adrilling operation without requiring breaking of the toolstring. In someembodiments, the ESD is capable of being recharged numerous timeswithout significant performance degradation, e.g., more than 10, 100,1,000, 10,000, or more times.

As shown in FIG. 41A, a toolstring 4100 may include multiple tools 4101connected to a TPB 4102. The toolstring 4100 may also include powersource 4103 (e.g., a battery or generator) connected to the TPB. Asshown in FIG. 41A, prior to inclusion of the power systems disclosedherein, each tool obtains electrical power from the power source 4103distributed through the TPB 4102.

The downhole power source 4103 may have limitations (e.g., voltage,current, peak power, etc.) that fall short of the requirements of one ormore of the tools 4101 (e.g., where one of the tools requires high peakpower, such as an EM or mud pulse telemetry tool, or one of the otherhigh power instruments mentioned above).

Some embodiments may use a topside power source (not shown) in additionto or instead of the downhole power source 4103. However in someembodiments, the topside source may also fair to meet the outputrequirements of one or more tools.

To overcome the limitations of the power source 4103, one or more ESDsmay be incorporated in the toolstring 4100. FIG. 41B is a schematicdemonstrating the implementation of such an ESD power system to meet thepower requirements of the tool string 4100. As shown, a single ESD 4104is used to provide power to the tool 4101 labeled “Tool B.” However, itis to be understood that in various embodiments multiple ESDs may beused, each providing power to one or more tools 4101 in the toolstring4100.

As shown in FIG. 41B, an ESD 4104 is connected to a TPB 4102 whichdistributes power from the downhole power source 4103. In variousembodiments, power will be input into the ESD 4104 through the TPB 4102at relatively low voltage, current, and/or power. For example, in someembodiments, the ESD 4104 receives input voltage and power at about 20 Vto about 50 V and about 20 w to 100 W, respectively.

In various embodiments, the ESD can store energy, e.g., 100 J to 10 kJor more or energy, and provide output (e.g., a pulsed output) at arelatively high voltage, current and/or power. For example, the ESD mayprovide output at voltages of 30 V to 200 V or more, and/or may outputpower at voltages of 100 W to 10 kW or more. Thus in variousembodiments, the ESD may meet one or more requirements of the associatedTool B that could not be met by the TPB 4102 and power source 4103alone. In various embodiments, the ESD may provide the above describedperformance in harsh environments, e.g., at temperatures throughout therange of −40 degrees Celsius to 250 degrees Celsius, or any sub-rangethereof.

Various embodiments may include suitable devices for controlling thecharging and discharging of the ESD 4104 with power from power suppliedfrom the power source 4103 (or a topside power source, not shown) Forexample, any of the UCC charging circuits of the type described hereinmay be used. For example, a regulator may be included for regulating thepower supplied from the power source 4103 (or a topside power source,not shown). The regulator may be, e.g., power based, current based, orvoltage based.

Having thus described aspects of an ESD based power system, it is to beunderstood that various embodiments may be realized. For example, theESD based power system may include circuits that provide a state ofcharge monitoring a state of charge of the ESD or components thereof(e.g., an HTRESD, batter, ultracapacitor, or the like), and/or thedownhole power supple 4303 and components thereof.

In certain embodiments, an ESD power system may include any suitablecontrol circuitry, e.g., for drawing power from one or more of severalbattery packs arranged, for example, in a redundant configuration.

In certain embodiments, an ESD based power system may further include orbe coupled to a motor drive, e.g., of the type described above.

In certain embodiments, an ESD based power system may include varioussensors, such as pressure, temperature and vibration sensors, and thelike, which may provide output to control circuitry for controlling thesystem as appropriate. In some embodiments, these sensors may includesensors of the type described in International Publication No.PCT/US14/59775 filed Oct. 8, 2014, the entire contents of which areincorporated by reference. In various embodiments, an ESD based powersystem may include a MSID of the type described herein, e.g., forimplementing various types of control, monitoring, power distribution,and other techniques for the tool string 4100 and incorporated ESDs4104.

In general, the downhole power system disclosed herein is adapted foroperation in the harsh environment encountered downhole. For example,the ESD and the power system as a whole are, in some embodiments,adapted for operation in a temperature range from ambient temperaturesup to about 250 degrees Celsius, or even higher temperatures in certainembodiments. In various embodiments, the system may include any of thehigh temperature components described herein, and may be fabricatedsuing any of the techniques described herein.

For example, components and techniques that may be used in the powersystem described herein may include: bare die silicon andsilicon-on-insulator active devices, silicon carbide active powerdevices, high temperature rated and low temperature coefficient ceramicpassives (COG or NPO dielectrics), and high temperature magneticpassives. AN (aluminum nitride) ceramics may be used as a circuitsubstrate material for excellent thermal stability and thermalconductivity. Circuit interconnects may be formed of oxidation resistantAu traces. Bonding strategies may employ flip chip or Au or Al wirebonding for bare die active components using, for instance, AuGe hightemperature solder. In some embodiments, wire bonding is expected to beadvantageous over flip chip bonding due to the added mechanicalcompliance, especially in the presence of thermal expansion and shockand vibration.

High temperature circuit techniques may be employed, for example, toensure stability of feedback regulation circuits despite very widetemperature swings as passive circuit components used for frequencycompensation may vary in value. Low or essentially zero temperaturecoefficient circuit designs can be achieved by coupling negativetemperature coefficient resistors with conventional resistors, byclosely matching active devices and by relying on ratiometric (relative)rather than absolute sensing and control. For example, bandgap derivedvoltage references can be employed to cancel the effect of very widetemperature variations on set points in feedback regulation circuits.Temperature coefficient strategic component selections mitigate theseproblems as well, for instance CGO or NPO dielectric ceramic capacitorshave a relatively flat response to temperature across this range. Activedevice performance variations can be significantly mitigated by use ofsilicon-on-insulator (SOI) and silicon carbide (SiC) technology widelyavailable in both hermetic and bare die form.

Other high temperature materials, components and architectures as areknown in the art may be employed to provide for operability at aspecified (high) temperature. Silicon-on-insulator (SOI), SiliconCarbide (SiC), bare die components, ceramic PCB's, low temperaturecoefficient passives and high temperature, hi-rel solders may be usedthe electronic systems. Examples of such components are described hereinand, e.g., in PCT Publication No. WO2012162500, published Nov. 29, 2012and PCT Publication No. WO2013009729 published Jan. 17, 2013, each ofwhich is incorporated herein by reference in its entirety.

The power systems described herein can be arranged in a variety ofconfigurations within a toolstring. In certain embodiments, the powersystems described herein, such an ESD Power System, can be arranged tosatisfy different form factors for toolstrings, including probe- andcollar-mounted toolstrings. Described herein are ESDs and ESD-containingpower systems configured for different form factors. For example, invarious embodiments, the ESD based power systems described herein may beincluded in a tool string having an outer diameter of less than 36inches, 12 inches, 6, inches, 3 inches, 2 inches, 1.75 inches, 1.5inches, 1 inch, 0.5 inches, or less, e.g., in the range of 0.5 inches to36 inches, or any sub-range thereof.

Although in the examples above in the present section of theapplication, the ESD based power system was employed to meet the peakpower requirements of various tools, it is to be understood that thesystem may, additionally or alternatively, be used to provide for higherefficiency power and/or for continuous power in the presence of anintermittent power source, as described in greater detail above.

Designs of the Present Invention

Any designs that are novel for their aesthetic appearance, are intendedto be included as part of the present invention.

INCORPORATION BY REFERENCE

The entire contents of all patents, published patent applications andother references cited herein are hereby expressly incorporated hereinin their entireties by reference.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures described herein. Such equivalents were consideredto be within the scope of this invention and are covered by thefollowing claims. Moreover, any numerical or alphabetical rangesprovided herein are intended to include both the upper and lower valueof those ranges. In addition, any listing or grouping is intended, atleast in one embodiment, to represent a shorthand or convenient mannerof listing independent embodiments; as such, each member of the listshould be considered a separate embodiment.

In support of the teachings herein, various analysis components may beused, including a digital system and/or an analog system. The system(s)may have components such as a processor, storage media, memory, input,output, communications link (wired, wireless, pulsed mud, optical orother), user interfaces, software and firmware programs, signalprocessors (digital or analog) and other such components (such asresistors, capacitors, inductors and others) to provide for operationand analyses of the apparatus and methods disclosed herein in any ofseveral manners well-appreciated in the art. It is considered that theseteachings may be, but need not be, implemented in conjunction with a setof computer executable instructions stored on a computer readablemedium, including memory (ROMs, RAMs), optical (CD-ROMs), or magnetic(disks, hard drives), or any other type that when executed causes acomputer to implement the method of the present invention. Theseinstructions may provide for equipment operation, control, datacollection and analysis and other functions deemed relevant by a systemdesigner, owner, user or other such personnel, in addition to thefunctions described in this disclosure.

It should be recognized that the teachings herein are merelyillustrative and are not limiting of the invention. Further, one skilledin the art will recognize that additional components, configurations,arrangements and the like may be realized while remaining within thescope of this invention. For example, configurations of layers,electrodes, leads, terminals, contacts, feed-throughs, caps and the likemay be varied from embodiments disclosed herein. Generally, designand/or application of components of the ultracapacitor andultracapacitors making use of the electrodes are limited only by theneeds of a system designer, manufacturer, operator and/or user anddemands presented in any particular situation.

Further, various other components may be included and called upon forproviding for aspects of the teachings herein. For example, anadditional power supply (e.g., at least one of a generator, a wireline,a remote supply and a chemical battery), cooling component, heatingcomponent, pressure retaining component, insulation, actuator, sensor,electrodes, transmitter, receiver, transceiver, antenna, controller,electrical unit or electromechanical unit may be included in support ofthe various aspects discussed herein or in support of other functionsbeyond this disclosure.

While the invention has been described with reference to exemplaryembodiments, it will be understood that various changes may be made andequivalents may be substituted for elements thereof without departingfrom the scope of the invention. In addition, many modifications will beappreciated to adapt a particular instrument, situation or material tothe teachings of the invention without departing from the essentialscope thereof. Therefore, it is intended that the invention not belimited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention but to be construed by theclaims appended herein.

What is claimed is:
 1. A downhole power system comprising: a first energy storage device (ESD) positioned within a toolstring to provide power to one or more instruments within the toolstring; wherein the first ESD is configured operate at temperatures at or above 210 degrees C. to: receive power from a power source at a first power level that is lower than a power requirement of a first tool in the toolstring, and output power to the tool at a second power level that is at or above the requirement of the first tool in the toolstring.
 2. The system of claim 1, wherein the ESD receives power form the power source through a tool string power bus configured to provide power to one or more tools in the toolstring.
 3. The system of claim 2, wherein the first tool comprises at least one selected from the list consisting of: a nuclear magnetic resonance tool, a coring tool, a sonic tool, a neutron density tool, a gamma detector tool, a seismic measurement tool, a telemetry tool, a resistivity tool, and a formation tester.
 4. The system of claim 2, wherein the first ESD has an energy storage capacity in the range of 100 J to 100 kJ of energy.
 5. The system of claim 4, wherein the first ESD has an energy storage capacity of at least 1 kJ
 6. The system of claim 4, wherein the first ESD is configured to provide an output voltage in the range of 30 V to 200 V.
 7. The system of claim 4, wherein the first ESD is configured to provide an output power in the range of 50 W to about 100 kW.
 8. The system of claim 7, wherein the first ESD has a peak output power of at least 100 W.
 9. The system of claim 7, wherein the first ESD has a peak output power of at least 1 kW.
 10. The system of claim 7, wherein the first ESD has an operational temperature range of −40 degrees C. to 210 degrees C.
 10. The system of claim 7, wherein the first ESD has an operational temperature range of −40 degrees C. to 250 degrees C.
 11. The system of claim 7, wherein the first ESD comprises a high temperature rechargeable energy storage device (HTRESD).
 12. The system of claim 7, wherein the HTRESD an ultracapacitor.
 13. The system of claim 12, wherein the ultracapacitor has a volumetric power density of at least 50 kW/L.
 14. The system of claim 12, wherein the ultracapacitor has a volumetric power density of at least 100 kW/L.
 15. The system of claim 13, wherein the ultracapacitor is configured to operate at temperatures above 210 degrees Celsius for at least 10,000 charge/discharge cycles at a voltage of at least 0.5V while exhibiting and increase in equivalent series resistance (ESR) or less than about 100% and a decrease in capacitance of less than about 10%.
 16. The system of claim 1, wherein the first ESD is located adjacent to the first tool in the toolstring.
 17. The system of claim 1, wherein the power source comprises a downhole generator or downhole battery.
 18. The system of claim 1, further comprising: a second ESD positioned within a toolstring to provide power to one or more instruments within the toolstring; wherein the second ESD is configured operate at temperatures at or above 210 degrees C. to: receive power from a power source at a first power level that is lower than a power requirement of a second tool in the toolstring, and output power to the tool at a second power level that is at or above the requirement of the second tool in the toolstring.
 19. The system of claim 1, further comprising: a modular signal interface device (“MSID”) module for controlling at least one of the power provided to a downhole tool connected to the downhole power system and the charge-discharge cycles of the first ESD, wherein the MSID is adapted to connect to the power source.
 20. A method comprising: providing a first energy storage device (ESD) positioned within a toolstring to provide power to one or more instruments within the toolstring; operating the first ESD at temperatures at or above 210 degrees C. to: receive power from a power source at a first power level that is lower than a power requirement of a first tool in the toolstring, and output power to the tool at a second power level that is at or above the requirement of the first tool in the toolstring. 